Ketal ester derivatives

ABSTRACT

The present disclosure relates to the preparation of acrylate, alkacrylate, allyl, and polycarbonate derivatives of hydroxy ketal esters, and uses thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 61/099,922, entitled “Polymers from Hydroxy KetalCarboxylates”, filed on Sep. 25, 2008, which is incorporated byreference in its entirety herein; this application further claims thebenefit of U.S. Provisional Patent Application No. 61/147,278, entitled“Poly(vinyl chloride) Compositions Containing Compounds Derived FromKetal Esters, and Articles Therefrom”, filed on Jan. 26, 2009, which isincorporated by reference in its entirety herein; this applicationfurther claims the benefit of U.S. Provisional Patent Application No.61/179,460, entitled “Ketal Compounds and Uses Thereof”, filed on May19, 2009, which is incorporated by reference in its entirety herein;this application further claims the benefit of U.S. Provisional PatentApplication No. 61/219,098, entitled “Ketal Compounds and Uses Thereof”,filed on Jun. 22, 2009, which is incorporated by reference in itsentirety herein.

BACKGROUND

Many known monomers and polymers are currently synthesized fromnon-renewable, expensive, petroleum-derived or natural gas-derivedfeedstock compounds. High raw material costs and uncertainty of futuresupplies requires the discovery and development of useful monomers andpolymers that can be made from inexpensive renewable biomass-derivedfeedstocks and by simple chemical methods. Using renewable resources asfeedstocks for chemical processes will reduce the demand onnon-renewable fossil fuels currently used in the chemical industry andreduce the overall production of carbon dioxide, the most notablegreenhouse gas.

Polycarbonates, acrylate and alkacrylate monomers and polymers, allylmonomers and polymers, and oxirane (epoxy) monomers and polymers areuseful materials in making many industrially important formulations andarticles. It is desirable to provide acrylyl, alkacrylyl, oxiranyl, andallyl functional compounds, as well as their polymerized or graftedcounterparts, based in whole or in part upon renewable biomassfeedstocks. It is desirable to provide one or more linear, branched,crosslinked, or grafted materials based on renewable biomass feedstocksfor use various applications in order to replace or partially replacepetroleum based materials. It is desirable to provide polycarbonatesbased in whole or in part upon renewable biomass feedstocks, aspolycarbonates are useful for many known applications. It is desirableto provide such useful materials by employing simple chemicalmethodology that is easily implemented using known industrialmethodologies and processes.

SUMMARY

Disclosed herein are compounds including polycarbonates, allylicmonomers and polymerized or grafted products thereof, oxiranylfunctional monomers and polymerized or grafted products thereof, andacrylate and methacrylate monomers and polymerized or grafted productsthereof, derived from renewable biomass feedstocks. The compounds arebased on hydroxy ketal carboxylate Precursors, which have the structureof either Precursor P1 or Precursor P2. Precursor P1 has the structure:

wherein

-   -   R¹ is hydrogen or a monovalent, divalent, or multivalent linear,        branched, or cyclic alkyl or alkenyl group having 1 to 36 carbon        atoms, or an aryl or alkaryl group, wherein the alkyl, alkenyl,        or alkaryl group includes, in some embodiments, one or more        functional groups such as halogen, tertiary amine, hydroxyl,        carbonate, carboxylic acid, carboxylic ester, ether, carbonyl,        ketal, urethane, imide, amide, sulfone, sulfonamide, mercaptan,        phosphate, phosphonooxy, silane, or silyl;    -   R² is a covalent bond or a linear, branched, or cyclic alkyl,        alkenyl, or alkynyl group having 1 to 18 carbon atoms, or an        aryl or alkaryl group, wherein the alkyl, alkenyl, aryl, or        alkaryl groups include, in some embodiments, one or more        additional functional groups such as halogen, tertiary amine,        carbonate, ether, ester, carbonyl, urethane, imide, amide,        sulfone, sulfonamide, mercapto, disulfide, phosphate,        phosphonooxy, silane, or silyl;    -   R³ is hydrogen, alkynyl, or a linear, branched, or cyclic alkyl        or alkenyl group having 1 to 18 carbon atoms, or an aryl or        alkaryl group, wherein the alkyl, alkenyl, aryl, or alkaryl        groups include, in some embodiments, one or more additional        functional groups such as halogen, tertiary amine, carbonate,        ether, ester, carbonyl, urethane, imide, amide, sulfone,        sulfonamide, mercapto, disulfide, phosphate, phosphonooxy,        silane, or silyl;    -   R⁴ is silyl, silane, or siloxane, or a hydrocarbon group having        the formula

-   -   wherein a is 0 or 1 and R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are        independently hydrogen, alkynyl, or linear, branched, or cyclic        alkyl or alkenyl groups having 1 to 18 carbon atoms, or an aryl        or alkaryl group, wherein the alkyl, alkenyl, aryl, or alkaryl        groups include, in some embodiments, one or more additional        functional groups such as halogen, tertiary amine, carbonate,        ether, ester, carbonyl, urethane, imide, amide, sulfone,        sulfonamide, mercapto, disulfide, phosphate, phosphonooxy,        silane, or silyl;    -   α is an integer of 1 to about 100 and, where two values of α        exist on one molecule, the values of α may be the same or        different; and    -   β is an integer of about 1 to 10.        Precursor P2 has the structure:

wherein

-   -   R², R³, R⁴, and β are as defined for Precursor P1;    -   R¹¹ is a monovalent, divalent, or multivalent linear, branched,        or cyclic alkyl or alkenyl group having 1 to 36 carbon atoms, or        an aryl or alkaryl group, wherein the alkyl, alkenyl, aryl, or        alkaryl groups include, in some embodiments, one or more        additional functional groups such as halogen, tertiary amine,        carbonate, ether, carboxylic acid or ester, carbonyl, urethane,        imide, amide, sulfone, sulfonamide, mercapto, disulfide,        phosphate, phosphonooxy, silane, or silyl; or a ketal residue:

-   -   wherein R^(2′), R^(3′), and R^(4′) are as defined for R², R³,        and R⁴ respectively;    -   R¹² is hydrogen or a linear or branched alkyl group having        between 1 and 8 carbons; and    -   α is an integer of about 1 to 100, or where R¹¹ is a ketal        residue α is 0 or an integer of 1 to about 100; and where there        is more than one α, the values of α are the same or different.        Precursors P1 and P2 include compounds formed by the reaction of        diols or triols with oxocarboxylic acids, or esters thereof, to        form ketal esters and hydroxy ketal esters; in some embodiments,        this is followed by self condensation to form Precursors P1 and        P2 where α is 1 or more. Hydroxy ketal esters and the        self-condensation products thereof are described in Selifonov,        U.S. Patent Pub. No. 2008/0242721 and Wicks et al., PCT        Application No. WO 2009/032905, the contents of both which are        incorporated herein by reference in their entirety. Improved        methods of making various ketal esters are described in        Selifonov et al., PCT Application No. WO 2009/048874, the        contents of which are incorporated herein by reference in its        entirety. It will be understood that self-condensation of        hydroxy ketal esters results in a statistical mixture of        oligomeric and polymeric moieties; thus, where more than one α        is present for a single Precursor P1 or P2, values of α are the        same of different for each α and values of α are the same of        different for each individual molecule of P1 and P2.

Precursors P1 and P2 further include products of cocondensation ofhydroxy ketal esters with additional polyacids, polyols, or acombination thereof. Thus, for example, for Precursor P1 where β is 2,R¹ is the residue of a diol or the residue of the hydroxy-terminatedcondensation product of a diacid and a diol (e.g. a polyester polyol),optionally including one more hydroxy ketal esters or other difunctionalmonomers having both an ester or acid functionality and a hydroxylfunctionality (hydroxyacids or hydroxyesters, such as lactic acid or anester thereof) which is then further reacted with one or more hydroxyketal esters to form the Precursor. Such cocondensation products arealso described in Selifonov, U.S. Patent Pub. No. 2008/0242721 and Wickset al., PCT Application No. WO 2009/032905. Other Precursors P1 areeasily envisioned, including embodiments wherein R¹ is the residue of atriol and β is 3, thereby providing three hydroxyl moieties permolecule; or R¹ is the residue of a diol and β is 1, thereby providingtwo hydroxyl moieties per molecule. The Precursors P1 have in common oneor more hydroxyl endgroups that are employed to make the compounds ofthe invention. It will be understood that each hydroxyl present on amolecule of Precursor P1 is potentially available to undergo furtherreaction, as described below, to form a compound of the invention. So,for example, where R¹ has one or more additional hydroxylfunctionalities, those hydroxyls are also available, in embodiments, asprecursor hydroxyls for subsequent reactions in the same manner as thehydroxy ketal hydroxyl endgroup.

Similarly, Precursor P2 includes embodiments wherein β is 2, such thatR¹¹ is the residue of a diacid or the residue of the carboxyl-terminatedcondensation product of a diacid and a diol, optionally including onemore hydroxy ketal esters or other difunctional monomers having both anester or acid functionality and a hydroxyl functionality (hydroxyacidsor hydroxyesters, such as lactic acid or an ester thereof) which is thenfurther reacted with one or more hydroxy ketal esters or selfcondensates thereof to form the Precursor P2 . Such cocondensationproducts are also described in Selifonov, U.S. Patent Pub. No.2008/0242721 and Wicks et al., PCT Application No. WO 2009/032905. OtherPrecursors P2 are easily envisioned, including those wherein R¹¹ is theresidue of a triacid and β is 3. The Precursors P2 have in common one ormore carboxylic acid or ester endgroups that are employed to make thecompounds of the invention.

Precursors P2 also include, in embodiments, the group of compoundswherein R¹¹ is the residue of a ketal ester. Such compounds are thecondensation products of ketal esters with hydroxy ketal esters andcondensates of hydroxy ketal esters. For example, where R^(2′) is—(CH₂)₂—, R^(3′) is —CH₃, and R^(4′) is the residue of 1,2-propanediolor 1,2-ethanediol, R¹¹ is

One example of such a condensation product is

wherein α is an integer of between about 1 and 10, or in someembodiments a is between about 1 and 4. Such condensation products, andthe methods to make them, are disclosed in Mullen et al., U.S.Provisional Patent Application Nos. 61/179460 and 61/219098. Inembodiments, such Precursors P2 are plasticizers in a number of usefulPVC or other polymeric compositions and, in some such embodiments,impart properties to PVC that are similar to those imparted by thecommercially available plasticizer dioctyl phthalate. Other R^(4′)residues suitable for the current application include any of the known1,2- and 1,3-alkanediol compounds found in the literature. Examples ofsuitable 1,2- and 1,3-alkanediols include 1,2-ethanediol (ethyleneglycol), 1,2-propanediol (propylene glycol), 1,3-propanediol,2,2-dimethyl-1,3-propanediol(neopentyl glycol),3-mercaptopropane-1,2-diol (thioglycerol), dithiothreitol,1,2-butanediol, 1,3-butanediol, cyclohexane-1,2-diol,1,4-dioxane-2,3-diol, 3-butene-1,2-diol, indane-1,2-diol, tartaric acid,and 2,3-dihydroxyisovaleric acid. In some embodiments, 1,2-alkanediolsare synthesized by epoxidation of n-α-olefins such as 1-octene,1-hexene, 1-decene, and the like, followed by ring opening to form the1,2-diol. Such diols are also useful to form the alkylketal estersemployed to make the compounds of the invention. Preferred diols include1,2-propanediol and 1,2-ethanediol.

In embodiments where R¹¹ is a ketal residue, Precursors P2 also includethe group of compounds wherein α is 0; such compounds are referred toherein as ketal esters but can also be ketal acids in embodiments whereR¹² is hydrogen. The ketal esters include compounds such as

In some embodiments, the ketal ester embodiments of Precursor P2 areknown in the literature. For example, the 1,2-propanediol ketal of ethyllevulinate is disclosed athttp://www.thegoodscentscompany.com/data/rw1597311.html,

and the 1,2-propanediol ketal of ethyl acetoacetate is disclosed inHiramoto et al., U.S. Patent Publication No. 2006/0165622,

Precursors P2 also include the group of compounds wherein R¹¹ is theresidue of a dicarboxylic acid, tricarboxylic acid, or higherpolycarboxylic acid. In one such embodiment, where R² is —(CH₂)₂—, R³ is—CH₃, and R⁴ is the residue of glycerol, R¹¹ is the residue of adipicacid, β is 2, R¹² is —CH₂CH₃, α is an average of between 1 and 4, and βis 2, Precursor P2 is, in one embodiment,

In related embodiments, α and α′ are integers of between about 1 and100, or between about 1 and 10, or between about 1 and 4. The R¹² groupshave, in some embodiments, between about 1 and 8 carbons, or betweenabout 2 and 4 carbons. The above structure is formed from the glycerolketal of a levulinate ester, self condensed, and subsequently reactedwith a diacid or an ester thereof. Such diacids include, in variousembodiments, oxalic acid, malonic acid, succinic acid, adipic acid,pimellic acid, suberic acid, or sebacic acid, o, m, or p-phthalic acid,or any of the other known diacids or esters thereof. In otherembodiments, triacids such as trimellitic acid and cyclohexanetricarboxylic acid are used to form a trifunctional analog of the abovecompounds. Higher polyacids are also employed in some embodiments of theinvention, such that β, and number of carboxylic acid residues adjacentto R¹¹ of Precursor P2, is up to about 10. Such condensation products,and the methods to make them, are disclosed in Selifonov et al., U.S.Provisional Patent Application No. 61/147,278. In embodiments, suchPrecursors P2 are plasticizers in a number of useful PVC or otherpolymer compositions and, in some such embodiments, impart properties toPVC that are similar to those imparted by the commercially availableplasticizer dioctyl phthalate.

It will be understood that each carboxylate present on a molecule ofPrecursor P2 is potentially available to undergo further reaction, asdescribed below, to form a compound of the invention. So, for example,where R¹¹ has one or more additional carboxylic ester functionalities,those ester functionalities are also available, in embodiments, asprecursor esters for subsequent reactions in the same manner as thehydroxy ketal ester endgroups of Precursor P2.

Precursors P1 and P2 are, in some embodiments, biodegradable. In variousembodiments described below, the Precursors P1 and P2 enable the speciesof the invention to supply the desirable properties of associated withcommercially useful monomers, polymers, and grafted materials andadditionally supply biodegradability thereof. Additionally, PrecursorsP1 and P2 are capable of selective hydrolytic degradation at the ketallinkage. Ketal moieties undergo rapid and quantitative hydrolyticdegradation in the presence of strong mineral acid and water using mildtemperatures and pressures to produce a ketone and an alcohol. Thisselective degradation is accomplished, in embodiments, in the presenceof other functional groups such as esters, amides, alcohols, allylgroups, acrylates, carbonates, and ethers that remain intact. Theselective degradation of the ketal linkage of Precursors P1 and P2 isemployed in some embodiments described below to provide additionalfunctionality to one or more compounds of the invention, i.e. reactiveketone or hydroxyl groups for grafting reactions or compatibility and/ordesired differences in hydrophilicity. Also, the chemical degradationis, in some embodiments, advantageous for lithography applicationswherein a photo-acid generator (usually a strong acid) selectivelycleaves the labile ketal linkage to generate hydroxyl groups or ketonegroups for various applications. An additional advantage of selectivedegradation is that it enables, in embodiments, the breakdown of highmolecular weight adducts to lower molecular weight species for ease ofdisposal, recyclability, and/or degradation by erosion or thermal means.

In one embodiment, the compounds of the invention are polycarbonatesformed from Precursors P1 where β is 2, such that the polycarbonateshave one or more repeat units of structure IA or IB:

wherein

-   -   R¹, R², R³, and R⁴, and α are as defined for Precursor P1;    -   α′ is 0 or an integer of about 1 to 100; and    -   γ is an integer of about 1 to 30.        The repeat unit corresponding to IA is formed from Precursor P1        wherein β is 2; the repeat unit corresponding to IB is formed        from Precursor P1 wherein β is 1 and R¹ contains an hydroxyl        group. The polycarbonates I have, in embodiments, endgroups that        are hydroxyalkyl or alkylcarbonate. In some embodiments, the        polycarbonates I having two hydroxyl endgroups and are starting        materials in the synthesis of other compounds, such as        poly(carbonate urethane)s. In some embodiments, Precursors P1        wherein β is more than 2 are employed to form polycarbonates I.        In such embodiments, branched or crosslinked polycarbonates I        are formed.

In another embodiment, the compounds of the invention are acrylyl,alkacrylyl (such as methacrylyl), oxiranyl, or allyl functionalcompounds having the structure II:

wherein

-   -   R¹, R², R³, R⁴, α, and β are as defined for Precursor P1; and    -   R¹³ is acrylyl, alkacrylyl, glycidyl, allyl, or a linear,        branched, or cyclic alkyl, aryl, or alkaryl group that includes        an acrylyl, alkacrylyl, oxiranyl, or allyl moiety and can        further have one or more additional functional groups that can        include, for example, halogen, tertiary amine, carbonate, imide,        amide, sulfone, sulfonamide, urethane, mercapto, disulfide,        ether, phosphate, phosphonooxy, silane, or silyl.

In yet another embodiment, the compounds of the invention are oxiranylor allyl functional compounds having the structure III:

wherein

-   -   R¹¹, R², R³, R⁴, α, and β are as defined for Precursor P2; and    -   R¹⁴ is glycidyl, allyl, or a linear, branched, or cyclic alkyl,        aryl, or alkaryl group that includes an oxirane or allyl moiety        and can further have one or more additional functional groups        that can include, for example, halogen, tertiary amine,        carbonate, imide, amide, sulfone, sulfonamide, urethane,        mercapto, disulfide, ether, phosphate, phosphonooxy, silane, or        silyl.

In yet another embodiment, the compounds of the invention arepolymerized or grafted adducts formed from the compounds having thestructure II. Such adducts are represented by structure IV:

-   -   wherein    -   R¹, R², R³, R⁴, α, and β are as defined for Precursor P1; and    -   R¹⁵ is the residue of a polymerized or grafted acrylyl,        alkacrylyl, glycidyl, or allyl group, or a linear, branched, or        cyclic alkyl, aryl, or alkaryl group that includes the residue        of a polymerized or grafted acrylyl, alkacrylyl, oxiranyl, or        allyl moiety and can further have one or more additional        functional groups such as halogen, tertiary amine, carbonate,        imide, amide, sulfone, sulfonamide, urethane, mercapto,        disulfide, ether, phosphate, phosphonooxy, silane, or silyl.

And in yet another embodiment, the compounds of the invention arepolymerized or grafted adducts formed from the compounds having thestructure III. Such adducts are represented by structure V:

wherein

-   -   R¹¹, R², R³, R⁴, α, and β are as defined for Precursor P2; and    -   R¹⁶ is a repeat unit comprising the residue of a polymerized or        grafted glycidyl or    -   allyl group, or a linear, branched, or cyclic alkyl, aryl, or        alkaryl group that includes the residue of a polymerized or        grafted oxiranyl or allyl moiety and can further have one or        more additional functional groups such as halogen, tertiary        amine, carbonate, imide, amide, sulfone, sulfonamide, urethane,        mercapto, disulfide, ether, phosphate, phosphonooxy, silane, or        silyl.        In some embodiments, adducts IV and V are homopolymers; in other        embodiments adducts IV and V are copolymers. In some embodiments        adducts IV and V are incorporated into linear polymers; in other        embodiments adducts IV and V are incorporated into branched        polymers; in other embodiments adducts IV and V are incorporated        into a crosslinked polymer network; in still other embodiments        adducts IV and V are grafted to some other entity. As used        herein, “entity” means either a compound or surface. Nonlimiting        examples of entities include a solid macroscopic surface, such        as a glass windowpane surface or a thermoplastic automobile part        surface; a polymer; a coating; or a particle. In still other        embodiments, adducts IV and V are both polymerized and grafted,        for example where a copolymer is also grafted to a particle.        Adducts IV are formed from compounds II by employing known        techniques of polymerization or grafting of acrylate,        alkacrylate, allyl, or oxiranyl moieties. Adducts V are formed        from compounds III by employing known techniques of        polymerization or grafting of allyl or oxiranyl moieties.        Polymerization of compounds II and III to form adducts IV and V        include, in various embodiments, one or more comonomers; thus        adducts IV and V encompass copolymers thereof having        incorporated therein the residues of one or more suitable        comonomers.

The compounds of the invention having structures I, II, III, IV, and Vare, in embodiments, made in whole or in part from materials availablefrom renewable biomass sources. The compounds of the invention have, inembodiments, physical properties suitable for replacingpetrochemical-based materials in applications wherein thermoplastics orthermosets are usefully employed. Such applications include, withoutlimitation, coatings, films, fibers and woven or nonwoven fabrics,elastomeric members, adhesives and sealants, and monolithic articlessuch as lenses, food containers, furniture, and the like. Additionally,due to the biocompatibility of the major products formed on breakdown byacidic hydrolysis, these materials are useful, in some embodiments, forfabrication or coating of medical devices or as the matrix materials forcontrolled release of pharmaceutical or agro-chemical actives.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a synthetic scheme for synthesis of a compound of theinvention.

FIG. 2 shows a synthetic scheme for synthesis of a compound of theinvention.

FIG. 3A shows a synthetic scheme for synthesis of a compound of theinvention.

FIG. 3B shows an alternative synthetic scheme for the synthesis of acompound of the invention.

FIG. 4 shows a differential scanning calorimetry plot for a compound ofthe invention.

FIG. 5 shows a gas chromatograph for a compound of the invention.

FIG. 6 shows a gas chromatograph for a compound of the invention.

FIG. 7 shows a gel permeation chromatograph for a compound of theinvention.

FIG. 8 shows a differential scanning calorimetry plot for a compound ofthe invention.

FIG. 9 shows a differential scanning calorimetry plot for a compound ofthe invention.

FIG. 10 shows a differential scanning calorimetry plot for a compound ofthe invention.

FIG. 11 shows representative compounds of the invention and theirbiomass content.

DETAILED DESCRIPTION OF THE INVENTION

In embodiments, Precursors P1 as defined above wherein β is 2 are usefulfor making one or more polycarbonates IA; in other embodiments,Precursors P1 as defined above wherein β is 1 and R¹ contains at leastone hydroxyl group are useful for making one or more polycarbonates IB.Collectively, polycarbonates IA and IB are referred to as“polycarbonates I.” Such embodiments include polycarbonates I wherein ais 0; or wherein α is between about 1 and 100. Such embodiments alsoinclude polycarbonates I formed from Precursor P1 compounds wherein β isabout 3 to 10. Polycarbonates I are the reaction products of diesters ofcarbonic acid or phosgene (Cl₂C═O) with a Precursor P1 having at leasttwo hydroxyl moieties. In some such embodiments a linear ispolycarbonate formed; in other embodiments, including those whereinPrecursors P1 have β of 3 or more, a branched or crosslinked structureis formed.

In general, any of the techniques found in the literature that areuseful for making polycarbonates are also useful to make thepolycarbonates of the invention. In some embodiments, a Precursor P1compound is reacted with phosgene. In one such embodiment, the PrecursorP1 is reacted with aqueous sodium hydroxide to form the correspondingsodium salt. The aqueous phase is then contacted with an immiscibleorganic phase containing phosgene. A linear polymer is formed, inembodiments, at the interface between the aqueous and organic phases.One example of such a reaction is represented in FIG. 1, for a PrecursorP1 where a is 1, β is 2, R¹ is —(CH₂)₄—, R² is —CH₂—, R³ is —CH₃, and R⁴os the residue of 1,1,1-trimethylolethane, or

In some such embodiments, the sodium cation is exchanged for a moreorganic miscible cation, such as tetrabutylammonium and the like, priorto commencing the interfacial reaction. Tetraalkylammonium cations aresometimes referred to in the literature as phase transfer catalysts, andhave been observed to cause increased rates of interfacial reaction byincreasing the miscibility of the salt in the organic phase. In someembodiments of the invention, employing a phase transfer catalyst withthe Precursor P1 salts increases the rate of interfacial reaction toform the polycarbonates of the invention. In other embodiments, thePrecursor P1 structures and their sodium salts possess sufficientorganic miscibility that the use of phase transfer catalyst is notrequired to reach satisfactory rates of reaction.

In some embodiments, the polycarbonates of the invention are synthesizedby the reaction of a Precursor P1 with a diester of carbonic acid havingthe general structure

where R_(a) and R_(b) may be the same or different and representoptionally substituted aliphatic, ar-aliphatic or aromatic hydrocarbonradicals. The disubstituted carbonate esters can further containheteroatoms, such as halogen, nitrogen, or oxygen. Nonlimiting examplesof suitable dialkyl carbonates include dimethyl carbonate, diethylcarbonate, di-n-propyl carbonate, di-n-butyl carbonate, di-isobutylcarbonate, bis(2-bromoethyl) carbonate,bis(2,2,2-trichloroethyl)carbonate, ethyl(4-methylphenyl) carbonate,diphenyl carbonate, bis(2-methoxyphenyl)carbonate, bis(4-nitrophenyl)carbonate, dinaphthalen-1-yl carbonate, dibenzyl carbonate, and thelike.

In embodiments, carbonate diesters are employed to synthesize thepolycarbonates of the invention using any of the known techniques in theliterature for making polycarbonates from diols or higher polyols anddialkyl carbonates or diarylcarbonates. For example, Moethrath et al.,U.S. Patent Publication No. 2003/0204042 teach the synthesis of highmolecular weight aliphatic polycarbonates employing a two-stage processwherein a low molecular weight aliphatic polycarbonate is formed,followed by condensation of the low molecular weight adduct with adiaryl carbonate to give a high molecular weight final product. Inanother example, Schnell et al., German Patent No. DE 1 031 512 disclosethe synthesis of high molecular weight aliphatic polycarbonatesemploying diethyl carbonate and alkali catalysts in conjunction with abase-binding compound, such a phenyl chloroformate. The describedmethods are also useful to form the polycarbonates of the invention. Oneexample of such a reaction is represented in FIG. 1, employing PrecursorP1 where α is 1, β is 2, R¹ is —(CH₂)₄—, R² is —CH₂—, R³ is —CH₃, R⁴ isthe residue of 1,1,1-trimethyloethane, and R_(a) and R_(b) are phenyl.

In some embodiments, the polycarbonates I of the invention have valuesof γ of between 1 and about 30, corresponding to molecular weights ofabout 500 to about 30,000 g/mol, depending on the molecular weight ofPrecursor P1. In various embodiments, the polycarbonates of theinvention have a broad range of available properties due to the range ofcompounds I available, which in turn is due to the range of bothstructures and molecular weights of Precursor P1 compounds available. Insome embodiments, the polycarbonates I possess good toughness andthermal stability. In some embodiments the polycarbonates I aretransparent to visible light and possess good clarity and low color,e.g. are “water white.” In some embodiments, the combination oftoughness, thermal stability, and transparency make the polycarbonates Isuitable for a wide range of applications.

The polycarbonates I of the invention are synthesized, in preferredembodiments, from biomass-based feedstocks. The glycerol and1,1,1-trimethylolpropane ketals of levulinic and pyruvic acid, andesters thereof, are derivable or potentially derivable from biomasssources and do not require the use of petroleum based feedstocks. Also,carbonate precursors such as dialkylcarbonates are based in part onnon-petroleum sources. In embodiments, at least 20% by weight thepolycarbonates I are biomass based. In other embodiments, between about20% and 90% by weight the polycarbonates I are biomass based. In otherembodiments, between about 40% and 75% by weight the polycarbonates Iare biomass based. FIG. 11 shows a list of representative compounds ofthe invention and their biomass content by weight.

Another advantage of the polycarbonates of the invention is that they donot require the use of Bisphenol A (4,4′-dihydroxy-2,2-diphenylpropane),the most commonly employed polycarbonate polyol. Bisphenol A has beenthe subject of toxicity concerns since the 1930s, particularly in foodor drink contact applications (e.g., baby bottles, water/drink bottles,food containers). The polycarbonates of the invention, in one or moreembodiments, are useful in applications where it is desirable toeliminate some or all of the Bisphenol A commonly employed to makepolycarbonates. Additionally, the polycarbonates of the invention are,in some embodiments, biodegradable. Biodegradable polycarbonates areuseful for one or more applications, for example, in food or drinkcontact applications, to enable disposable embodiments of variouscontainers. Other applications where biodegradability is advantageousinclude disposable medical supplies such as eye shields and the like. Invarious embodiments, the polycarbonates of the invention advantageouslysupply the desirable properties of known polycarbonates and additionallysupply biodegradability thereof. Additionally, the polycarbonates I ofthe invention are, in some embodiments, capable of selective hydrolyticdegradation. In embodiments, ketal moieties undergo rapid andquantitative hydrolytic degradation in the presence of strong mineralacid and water using mild temperatures and pressures to produce a ketonemoiety and an alcohol. This selective degradation may be accomplished inthe presence of other functional groups such as esters, amides,alcohols, allyl groups, acrylates, carbonates, and ethers. This chemicaldegradation enables the break down of high molecular weightpolycarbonates Ito lower molecular weight species for ease of disposal,recyclability, and/or degradation by erosion or thermal means. Thischemical degradation is, in embodiments, also advantageous forlithography applications of the polycarbonates I in which a photo-acidgenerator (usually a strong acid) selectively cleaves the labile ketallinkage to generate hydroxyl groups or ketone groups for variousapplications.

In some embodiments, the polycarbonates I of the invention areterminated by two hydroxyl endgroups. Such compounds I are suitable asdiols for use in polyurethane synthesis. In some such embodiments,polycarbonates I having values of γ of 1 to about 30 and two hydroxylendgroups are, in embodiments, useful as feedstocks for synthesis ofpolyurethanes. Such polycarbonate I diols are synthesized, in someembodiments, by controlling stoichiometry of the polycarbonatepolymerization in order to provide hydroxy ketal ester functionality orhydroxyalkyl at the ends of the polycarbonate. Polycarbonates havinghydroxyl endgroups are, in embodiments, reacted with one or morediisocyanates to form a polyurethane that is a poly(carbonate urethane).Poly(carbonate urethane)s of the invention are synthesized using any ofthe known techniques in the literature that are employed to makepolyurethanes from polyols and employ known diisocyanates in thereactions. In some such embodiments, techniques used to form thepoly(carbonate urethane)s of the invention are those outlined in Mooreet al., Novel Co-Polymer Polycarbonate Diols for Polyurethane ElastomerApplications, Proceedings of the Polyurethanes Expo 2003, Oct. 1-3, 2003(© 2003, American Chemistry Council).

Suitable diisocyanates useful in reactions with the hydroxyl groups ofthe polycarbonate diols of the invention include, without limitation,those represented by formula OCN—Z—NCO, in which Z represents a divalentaliphatic hydrocarbon group having 4 to 18 carbon atoms, a divalentcycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, a divalentaralkyl group having 7 to 15 carbon atoms, or a divalent aromatichydrocarbon group having 6 to 15 carbon atoms. Non-limiting examples ofsuitable organic diisocyanates include 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylenediisocyanate, 1,12-dodecamethylene diisocyanate,cyclohexane-1,3-diisocyanate, cyclohexane -1,4-diisocyanate,1-isocyanato-2-isocyanatomethyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl) methane,2,4′-dicyclohexyl-methane diisocyanate, 4,4′-dicyclohexyl-methanediisocyanate, 1,3-bis-(isocyanatomethyl)-cyclohexane,1,4-bis-(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)methane, α,α,α′,α′-tetramethyl-1,3-xylylene diisocyanate,α,α,α′,α′-tetramethyl-1,4-xylylene diisocyanate,1-isocyanato-l-methyl-4(3)-isocyanatomethyl cyclohexane,2,4-hexahydrotolylene diisocyanate, 2,6-hexahydrotolylene diisocyanate,1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylenediisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethanediisocyanate, 2,4′-diphenylmethane diisocyanate , 4,4′-diphenylmethanediisocyanate, 1,5-diisocyanato naphthalene; and mixtures thereof. Alsosuitable for reactions with polycarbonate diols are polyisocyanatescontaining 3 or more isocyanate groups. Nonlimiting examples of suitablepolyisocyanates include 4-isocyanatomethyl-1,8-octamethylenediisocyanate, aromatic polyisocyanates such as 4,4′,4″-triphenylmethanediisocyanate, and polyphenyl polymethylene polyisocyanates obtained byphosgenating aniline/formaldehyde condensates.

The Precursor P1 compounds defined above are useful, in variousembodiments, for the synthesis of acrylyl or alkacrylyl compounds II. Inembodiments, Precursor P1 compounds as defined above wherein β is 1 areuseful for making one or more acrylyl or alkacrylyl compounds II; inother embodiments, Precursor P1 compounds as defined above wherein β isbetween 2 and about 10, or those wherein R¹ further contains one or morehydroxyl groups, are useful for making one or more acrylyl or alkacrylylcompounds II. Such embodiments include Precursor P1 compounds wherein ais 0; or wherein a is between about 2 and 100. Any of the Precursors P1described above wherein the compound has at least one hydroxylfunctionality are, in embodiments, functionalized with one or moreacrylic or alkacrylic functionalities to form the acrylyl or alkacrylylcompounds of the invention. As used herein, the term “alkacryl-” means“methacryl-”, “ethacryl-” or any other alkylated vinyl moiety adjacentto a carboxylate moiety, wherein the vinyl moiety is capable ofsubsequent addition-type initiation and propagation.

Acrylic or alkacrylic functionality is imparted, in embodiments, to thehydroxy moieties of a Precursor P1 compound by employing conventionaltechniques for the reaction of alkanols to form acrylates oralkacrylates. The techniques and various compounds employed in suchreactions are widespread in the literature. In one embodiment, aPrecursor P1 having at least one free hydroxyl group is employed in anesterification reaction with acrylic acid or alkacrylic acid to form thecorresponding acrylate or alkacrylate compound II and water. In somesuch embodiments, a strong protic acid such as HCl, H₂SO₄ and the likeis employed to catalyze the esterification reaction. In some suchembodiments, water is removed from the reaction vessel using a knowntechnique such as evaporation or adsorption, e.g. by molecular sieves,in order to drive the reaction to high yield. In another embodiment,acrylyl chloride or alkacrylyl chloride is reacted with a Precursor P1having at least one free hydroxyl group to form the correspondingacrylic or alkacrylic compound II and hydrochloric acid (HCl). In somesuch embodiments, the HCl is scavenged by reaction with a basiccompound, for example ammonia, pyridine or triethylamine, to drive thereaction toward product by removing HCl as it forms and prevent unwantedside reactions or corrosive emissions. In yet another embodiment, anester of acrylic acid or alkacrylic acid, for example methyl acrylate orethyl methacrylate, is transesterified with one or more hydroxylmoieties present on a Precursor P1 compound to give the acrylate oralkacrylate compound II and the corresponding alkanol. In some suchembodiments, a strong protic acid (e.g. HCl, H₂SO₄), a Lewis acid suchas a titanium (IV) alkoxide, a strong base such as a metal alkoxide(e.g. sodium methoxide) or another compound known to be atransesterification catalyst is employed to catalyze the reaction. Thealkanol is, in embodiments, removed from the reaction vessel using aknown technique such as evaporation or adsorption in order to drive thereaction to high yield. An example of each of these three reactions isrepresented in FIG. 2, for a Precursor P1 where a is 0, β is 1, R¹ is—(CH₂)CH₃, R² is —(CH₂)₂—, R³ is —CH₃, and R⁴ is the residue ofglycerol.

It will easily be understood upon inspection of the Precursor P1structure that where β is 1, a single hydroxyl moiety present on thePrecursor P1 results in synthesis of a monofunctional acrylate oralkacrylate II employing one of the methodologies outlined above; and inembodiments where the Precursor P1 has β of 2 or more, and thus 2 ormore hydroxyl moieties, more than one acrylic or alkacrylicfunctionality may be imparted to the compound II. In general, acrylatesor alkacrylates II are useful for linear polymerization orcopolymerization when β is 1, and are useful for branching orcrosslinking reactions when β is 2 or more.

In a related reaction, Barbeau, et al., Journal of Polymer Science PartB: Polymer Physics, 38(21), 2750-68 (2000), disclose a reaction schemefor a compound having isocyanate endgroups that are subsequentlyendcapped with an acrylate group. This reaction scheme is suitablyemployed to form one or more compounds of the invention. Thus, inembodiments, hydroxyl moieties of a Precursor P1 may be functionalizedwith isocyanate groups, then further reacted with a hydroxy-functionalacrylate or alkacrylate to form an acrylate or alkacrylate II. Forexample, in one such embodiment, a Precursor P1 having β of 1 is reactedwith a diisocyanate to form a urethane moiety with a terminal isocyanatemoiety; in a subsequent reaction, the terminal isocyanate is reactedwith a 3-methacrylyl-2-hydroxylpropyl ester to give the correspondingacrylic prepolymer. Suitable diisocyanates useful in reactions with thehydroxyl groups of the Precursors P1 include, without limitation, thoserepresented by formula OCN—Z—NCO and related compounds as are describedabove. In embodiments where the Precursor P1 has β of 2, the twohydroxyl moieties are reacted with two molar equivalents of adiisocyanate, followed by reaction with 2-hydroxypropyl acrylate to givethe corresponding diacrylate. In yet another variation of thischemistry, an isocyanate endcapped material is crosslinked with ahydroxy-functional acrylate polymer, such as poly(2-hydroxypropylacrylate) or poly(vinyl alcohol); see, for example, Decker et al.,Macromol. Mater. Eng. 286, 5-16 (2001). Thus, in some embodiments, aPrecursor P1 is isocyanate capped and then functionalized with anacrylate polymer using the method of Decker et al. or a similar methodthat forms one embodiment of an adduct IV of the invention.

The acrylates and alkacrylates II and adducts thereof IV of theinvention are synthesized, in preferred embodiments, from biomass-basedfeedstocks. For example, the glycerol and 1,1,1-trimethylolpropaneketals of levulinic and pyruvic acid, and esters thereof, that form thePrecursors P1 are derivable or potentially derivable from biomasssources and do not require the use of petroleum based feedstocks. Thus,the current invention enables the synthesis of a biomass based set ofacrylate monomers, polymers, crosslinkers, and grafted materials;acrylate and methacrylate materials are well known to be industriallyuseful in a wide variety of applications. In embodiments, at least 20%by weight of the acrylates and alkacrylates II and adducts thereof IVare biomass based. In other embodiments, between about 20% and 90% byweight of the acrylates and alkacrylates II and adducts thereof IV arebiomass based. In other embodiments, between about 40% and 75% by weightof the acrylates and alkacrylates II and adducts thereof IV are biomassbased. FIG. 11 shows a list of representative compounds of the inventionand their biomass content by weight.

The acrylates and alkacrylates II of the invention are advantageouslyemployed in a variety of subsequent polymerization, grafting, and/orcrosslinking reactions to result in a final article incorporating one ormore acrylic or alkacrylic adducts IV of the invention. Thepolymerization, grafting, and/or crosslinking reactions are broughtabout by initiation and propagation of free radical, ionic, or redoxreactions to result in addition products of the vinyl unsaturated moietyof the acrylyl or alkacrylyl groups, using well known and characterizedreactions in the literature. Such reactions are widely used in theindustry and the acrylates and alkacrylates II are, in variousembodiments, reacted using any of the known techniques of polymerizationor crosslinking of acrylate functionalities to form adducts IV. Numerousreferences are available that discuss these techniques. Radicalpolymerization or crosslinking reactions initiated by thermal, redox,electromagnetic radiation such as ultraviolet (UV), or electron beam(ebeam) are the most common of these known techniques. Some usefulreferences discussing such means of polymerization of acrylatefunctional materials are Decker et al., Macromol. Mater. Eng. 286, 5-16(2001); Burlant, W., U.S. Pat. No. 3,437,514; Endruweit, et al., PolymerComposites 2006, 119-128; Decker, C., Pigment and Resin Technology30(5), 278-86 (2001); and Jönsson et al., Progress in Organic Coatings27, 107-22 (1996). There are a number of known methods of incorporatingmolecules having acrylic functionality in one or more radicallypolymerizable formulations, e g admixing, prepolymerization to form asyrup of coatable viscosity, followed by final reaction andcrosslinking, and the like. Some commonly used methods are those taughtby U.S. Pat. Nos. 3,437,514; 3,528,844; 3,542,586; 3,542,587; 3,641,210;and 3,642,939. Any of the techniques employed in these references may beadvantageously employed to bring about the reaction of acrylates andalkacrylates II of the invention, resulting in linear, branched,crosslinked, or grafted acrylic and alkacrylic polymers IV of theinvention.

Many useful formulations employing the acrylates and alkacrylates II andadducts IV thereof are readily envisioned. For example, in oneembodiment, a compound II of the invention having two or more acrylateor alkacrylate moieties is employed as a crosslinker, when blended withadditional vinyl compounds, and the unsaturated sites are reacted usinga known addition reaction mechanism. In other embodiments, a blend ofacrylates and alkacrylates II with one or more additional vinylcompounds are provided in a formulation that is coatable, sprayable, orotherwise applied to a surface and then reacted using a known additionreaction mechanism. “Vinyl compounds” include those compounds having oneor more acrylate, alkacrylate, acrylamide, or alkacrylamide residues.Non-limiting examples of additional vinyl compounds include acrylicacid, methacrylic acid, acrylamide, methacrylamide, N-hydroxymethylacrylamide, methacryloxyethyl phosphate, acrylonitrile,methacrylonitrile, 2-acrylamido-2-methylpropanesulfonic acid and saltsthereof; maleic acid, its salt, its anhydride and esters thereof;monohydric and polyhydric alcohol esters of acrylic and alkylacrylicacid such as 1,6 hexane diol diacrylate, neopentyl glycol diacrylate,1,3 butylene dimethacrylate, ethylene glycol diacrylate,trimethylolpropane triacrylate, pentaerythritol triacrylate,pentaerythritol tetracrylate, etc.; other oxygenated derivatives ofacrylic acid and alkylacrylic acids, e.g., glycidyl methacrylate,hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc.; halogenatedderivatives of the same, e.g., chloroacrylic acid and esters thereof;and diacrylates and dimethacrylates, e.g., ethylene glycol diacrylate.In some embodiments, the additional acrylate or alkacrylate compoundsare present in blends of between about 1 and 50 mole percent withcompounds II, or between about 1 and about 40 mole percent withcompounds II.

“Vinyl compounds” also include non-acrylate or alkacrylate functionalα,β-unsaturated compounds capable of copolymerizing with the acrylate oralkacrylate compounds II of the invention. Non-limiting examples ofnon-acrylate or alkacrylate functional α,β-unsaturated compounds includearomatic compounds such as styrene, methyl substituted styrenes such asa-methyl styrene, vinyl toluene, t-butyl styrene, chlorostyrene, divinylbenzene, and the like; aliphatic vinyl compounds such as ethylene,propylene, and α-olefins such as 1-octene, and the like, and allyl,bisallyl, and polyallyl compounds such as prop-2-enyl heptanoate,prop-2-enoxybenzene, prop-2-enyl acetate, allyl vinyl ether, allylmethyl ether, bisallyl ether, allyl adipate, diallyl carbonate,pentaerythritol tatraallyl ether,1-N,4-N-bis(prop-2-enyl)benzene-1,4-dicarboxamide, and the like. Otheradditional vinyl compounds useful in blends with the acrylic prepolymersof the invention are divinyl and tetravinyl compounds disclosed in U.S.Pat. Nos. 3,586,526; 3,586,527; 3,586,528; 3,586,529; 3,598,530;3,586,531; 3,591,626; and 3,595,687.

In embodiments, copolymerization of acrylates and alkacrylates II withone or more additional vinyl compounds results in acrylate andalkacrylate adducts IV that are copolymers having the residues of theone or more additional vinyl compounds incorporated therein. Theproperties and applications of such copolymers, as well as the biomasscontent thereof, are not limited in scope.

It will be easily understood that the means used to form acrylate andalkacrylate adducts IV, and blends thereof, from acrylates andalkacrylates II are not particularly limited. Thus, acrylates andalkacrylates II, or blends thereof with additional vinyl compounds, maybe reacted to form linear, branched, crosslinked, or grafted acrylateand alkacrylate adducts IV using any of the known radical, redox, ionic,coordination, or group transfer polymerization techniques that aregenerally known in the literature. These techniques include anionic andcationic polymerization techniques; living radical polymerizationtechniques; coordination polymerization techniques; and group transferpolymerization techniques. Such techniques result, in embodiments, inthe formation of unique and advantageous architecture, leading todesirable properties in the finished articles formed using the acrylicprepolymers of the invention. In some embodiments, the acrylates andalkacrylates II and blends containing them are processed, for example bycoating, extruding, mold filling, and so forth, with or withoutadditional solvents, prior to subsequent reaction of the acrylate oralkacrylate moieties. In some embodiments, the acrylates andalkacrylates II are blended with one or more additional acryliccompounds and/or additional vinyl compounds. After processing, theblends are reacted to form a linear, branched, crosslinked, or graftedacrylate or alkacrylate adduct IV.

In embodiments, acrylates or alkacrylates II are subjected to conditionsunder which they are grafted to a polymer or a surface to form graftedadducts IV. For example, Engle et al., U.S. Pat. No. 5,888,290 disclosea method of grafting acrylate polymers to silica surfaces employingchain transfer techniques in conjunction with polymerization of acrylatemonomers. In another example, Bilkadi et al., U.S. Pat. No. 5,677,050disclose a method of grafting acrylate polymers to silica surfacesemploying functionalization of silica with acrylate groups inconjunction with polymerization with acrylate monomers. Such methods areuseful, employing the acrylates and alkacrylates II, to provide particlegrafted acrylate or alkacrylate adducts IV, but are also easily adaptedto provide a grafted solid macroscopic surface, or a grafted coatingsurface, similarly functionalized with chain transfer agents or acrylategroups. Other techniques employed in the literature may also be used tocause acrylates or alkacrylates II to form grafted adducts IV.

The acrylate or alkacrylate adducts IV of the invention are thermosetsor thermoplastics. It will be readily understood that the properties ofacrylate or alkacrylate adducts IV vary greatly depending on thechemical structure of the Precursor P1 compounds used, molecular weightof the acrylate or alkacrylate adducts IV, crosslink density, and thecontent and structure of any additional vinyl compounds incorporatedtherein to form copolymers. In embodiments, formulations includingacrylates or alkacrylates II include a thermal or UV reactive freeradical initiator or another initiator such as an ionic or redoxinitiator, an additional vinyl compound, a chain transfer agent, afiller, a toughener, a solvent, a polymer, a surfactant, a UVstabilizer, a thermal stabilizer, an antioxidant, a colorant, aplasticizer, or a bleaching compound, or a combination of two or morethereof The formulations are, in embodiments, suitable for coating,spraying, thermoforming, or cutting. Formulations derived from compoundsII are useful in many industrially useful applications. Suchapplications include formulation of sprayable, coatable, or otherwisecure-in-situ adhesives, coatings, laminates, monolithic articles such astransparent panes for window applications, films, fibers, foams, and thelike. Formulations including polymerized or grafted acrylates oralkacrylate adducts IV are useful when incorporated into adhesives,coatings, laminates, monolithic articles such as transparent panes forwindow applications, films, fibers, foams, and the like. Suchformulations are formed in either in-situ from formulation componentsincluding acrylates and alkacrylates II, or are formed by blendingpolymerized or grafted acrylates or alkacrylate adducts IV with one ormore components such as a filler, a solvent, a polymer, a tackifier, atoughener, a surfactant, a UV stabilizer, a thermal stabilizer, anantioxidant, a colorant, a plasticizer, or a bleaching compound, or acombination of two or more thereof Blending is accomplished eitherbefore or after polymerization to form the polymerized adduct.

Additionally, the acrylates and alkacrylates II and adducts thereof IVof the invention are, in some embodiments, biodegradable. Biodegradableacrylates and alkacrylates compounds are useful for one or moreapplications, for example, in film applications for disposable films.Other applications where biodegradability is advantageous includedisposable medical supplies such as eye shields and the like. In variousembodiments, the acrylates and alkacrylates II and adducts thereof IV ofthe invention advantageously supply the desirable properties of knownacrylate and methacrylate monomers, polymers, and grafted materials andadditionally supply biodegradability thereof Additionally, the acrylatesand alkacrylates II and adducts thereof IV are, in some embodiments,capable of selective hydrolytic degradation at the ketal linkage. Ketalmoieties undergo rapid and quantitative hydrolytic degradation in thepresence of strong mineral acid and water using mild temperatures andpressures to produce a ketone and an alcohol. This selective degradationis accomplished, in embodiments, in the presence of other functionalgroups such as esters, amides, alcohols, allyl groups, acrylates,carbonates, and ethers that remain intact. The selective degradation ofthe ketal linkage in the polymerized acrylate and alkacrylate adducts IVis employed in some embodiments to provide additional functionality tothe polymer, i.e. ketone or hydroxyl groups for further graftingreactions or compatibility and/or desired differences in hydrophilicity.Also, this chemical degradation may be advantageous for lithographyapplications of the polymerized acrylate and alkacrylate adducts IV inwhich a photo-acid generator (usually a strong acid) selectively cleavesthe labile ketal linkage of the acrylate and alkacrylate adducts IV togenerate hydroxyl groups or ketone groups for various applications. Anadditional advantage of selective degradation is that it enables, inembodiments, the breakdown of high molecular weight adducts to lowermolecular weight species for ease of disposal, recyclability, and/ordegradation by erosion or thermal means.

The Precursors P1 are useful, in various embodiments, in the synthesisof allyl compounds II. As used herein, the term “allyl” or “allylfunctionality” means a —CH₂—CH═CH₂ moiety that is capable of subsequentpolymerization or crosslinking reactions utilizing a free radicalmechanism. Such embodiments include those employing Precursor P1compounds wherein a is 0 or wherein a is between about 1 and 100. Suchembodiments also include Precursor P1 compounds wherein β is 1; orwherein β is about 2 to 10.

In some embodiments, the one or more hydroxyl moieties of Precursor P1are functionalized with isocyanate groups, then further reacted withallyl alcohol to form an allyl terminated compound II. For example, inone such embodiment, a Precursor P1 having β of 2 is reacted with twoequivalents of a diisocyanate to form two urethane linkages having twoterminal isocyanate moieties; in a subsequent reaction, the terminalisocyanates are reacted with allyl alcohol to give the correspondingoxiranyl compound II. Suitable diisocyanates useful in reactions withthe hydroxyl groups of the Precursors P1 include, without limitation,those represented by formula OCN—Z—NCO and related compounds as aredescribed above. In another embodiment, the one or more hydroxylmoieties of Precursor P1 are reacted with allyl chloroformate to givethe allylcarbonate adduct of P1. In embodiments, such reactions arecarried out without an external catalyst; however, it is advantageous insuch embodiments to employ a trialkylamine or pyridinium compound, suchas triethylamine or pyridine, to scavenge the HCl that is a product ofthe addition reaction.

Precursor P2 compounds are also useful, in various embodiments, in thesynthesis of allyl compounds III. Such embodiments include Precursor P2compounds wherein α is 0 or wherein α is between about 1 and 100. Suchembodiments also include Precursor P2 compounds wherein β is 1; orwherein β is about 2 to 10. Allyl alcohol is employed, in embodiments,to synthesize allyl esters III from one or more Precursors P2 byesterification or transesterification reaction using any of the knowntechniques commonly employed to esterify or transesterify a carboxylicacid or ester thereof with an alcohol. For example, allyl alcohol isemployed in a esterification reaction of Precursor P2 wherein R¹² ishydrogen, and/or wherein R¹¹ further comprises a carboxylic acid moiety,by employing the methods of Kropa, U.S. Pat. No. 2,249,768. In otherembodiments, allyl alcohol is employed in the transesterification of aPrecursor P2 wherein R¹² is a linear or branched alkyl group havingbetween 1 and 8 carbons and/or wherein R¹¹ further comprises acarboxylic ester moiety. Suitable methods of transesterification to formallyl esters III from Precursors P2 are disclosed in Remme et al.,Synlett 2007, 3, 491-3 and Ruszkay et al., U.S. Pat. No. 5,710,316;other suitable methods are disclosed in Singh et al., J. Org. Chem.2004, 69, 209-12 and Chavan et al., Synthesis 2003, 17, 2695-8. Allylmonohalides are also suitably employed, in some embodiments, tosynthesize compounds III from Precursors P2 by employing a palladiumhalide or platinum halide catalyst, as disclosed by Brady, U.S. Pat. No.3,699,155.

The allyl compounds II and III are, in embodiments, polymerized,copolymerized, or grafted to form adducts IV and V, respectively, usingany of the techniques known in the literature to polymerize or graftallyl functional monomers. In embodiments, formulations comprising allylcompounds II and III include a free radical initiator, an additionalvinyl compound as defined above, a chain transfer agent, a filler, asolvent, a polymer, a surfactant, a UV stabilizer, a thermal stabilizer,an antioxidant, a colorant, a plasticizer, or a bleaching compound, or acombination of two or more thereof. The formulations thereby formed are,in embodiments, suitable for coating, spraying, thermoforming, orcutting. Formulations derived from allyl compounds II and III are usefulin many applications. Such applications include formulation ofsprayable, coatable, or otherwise cure-in-situ adhesives, coatings,laminates, monolithic articles such as transparent panes for windowapplications, films, fibers, foams, and the like. In some embodiments,heating an allyl compound II and optionally one or more additional vinylmonomers in the presence of a thermal free-radical initiator results inan allyl adduct IV; similarly, heating an allyl compound III andoptionally one or more additional vinyl monomers in the presence of athermal free-radical initiator results in an allyl adduct V. Typically,allyl polymers are made by charging one or more allyl monomers and afree-radical initiator to a reactor, and heating the mixture at atemperature effective to polymerize the monomer. This approach isdisclosed, for example, in “Kirk-Othmer Encyclopedia of ChemicalTechnology,” 4^(th) ed., Volume 2, pp. 161-179. Improved methods ofpolymerizing allyl compounds are also usefully employed with the allylcompounds II and III of the invention. For example, U.S. Pat. No.5,420,216 discloses that gradual addition of initiator is key to highconversion in allyl polymerization. Any such techniques may be employedto form linear, branched, crosslinked, or grafted allyl adducts IV or Vfrom allyl compounds II and III, respectively. Grafting of allylcompounds II and III to give grafted allyl adducts IV and V areaccomplished, in some embodiments, employing the techniques similar tothose employed to graft acrylate compounds to particles and surfaces asdisclosed in Engle et al., U.S. Pat. No. 5,888,290 and Bilkadi et al.,U.S. Pat. No. 5,677,050, or other techniques employed in the literature.In some embodiments of the invention, allyl compounds II or III haveβ=1, such that there is one allyl moiety per molecule; in otherembodiments of the invention allyl compounds II or III have β=1 and R¹¹includes an allyl ester, such that there are two allyl moieties permolecule. In some such embodiments the compounds II and III havesufficient reactivity to provide high conversion or high molecularweight in the resulting allyl polymeric or grafted adduct IV or V. Inother embodiments, allyl compounds II or III have β=2 or more, such thatthere are at least two allyl moieties per molecule. In some embodimentsthe allyl compounds II or III yield a solid, high molecular weight allyladduct IV or V by initiation with a suitable free-radical initiator.Such embodiments are useful to provide, for example, heat-resistant castsheets and thermoset moldings. In some such embodiments, the reactivityof compounds having more than one allyl group per molecule of allylcompound II or III facilitates formation of allyl adducts IV or V in twostages: a solid allyl compound II or III is molded by heating; thencompletion of the heat cycle gives an allyl adduct IV or V of superiorheat resistance. In embodiments, the relatively slow rate of reactionencountered with allyl groups compared to e.g. the polymerization ofvinyl or acrylate groups allows for greater control of the reaction, toresult in soluble “prepolymers”, e.g. partially reacted hybrid moleculeshaving chemical moieties attributable to both compounds II and IV, orIII and V; that is, the hybrid molecules are partially polymerized andcontain some reactive double bonds and some polymerized adducts. Allyladducts IV and V of the invention are thermoset or thermoplastic,depending on the degree of crosslinking. It is readily understood thatthe properties of allyl adducts IV and V vary greatly depending on boththe chemical structure of the Precursor P1 or P2 compounds used,molecular weight of the allyl adducts IV and V, crosslink or graftingdensity, and structure and content of any additional vinyl compoundresidues incorporated into allyl copolymer adducts IV and V.

One useful embodiment of the allyl compounds II and III of the inventionemploys minor proportions of polyfunctional allyl compounds II and III,wherein β is 2 or more, for cross-linking or curing preformed vinyl-typepolymers via grafting mechanism. Among the preformed polymers cured byminor additions of polyfunctional allyl compounds and catalyst, followedby heat or irradiation, are polyethylene, PVC, andacrylonitrile-butadiene-styrene (ABS) copolymers. In other embodiments,small proportions of mono- or polyfunctional allyl compounds II or IIIare added as regulators or modifiers of vinyl polymerization forcontrolling molecular weight and polymer properties. In yet otherembodiments, allyl compounds II and III having β is 2 or more arestabilizers against oxidative degradation and heat discoloration ofpolymers into which they are incorporated. A useful embodiment ofthermoset allyl adducts IV and V of the invention is in moldings andcoatings for electronic devices requiring high reliability underlong-term adverse environmental conditions. These devices includeelectrical connectors and insulators in communication, computer, andaerospace systems. Other embodiments are readily envisioned.Formulations for applications such as those above, for example,typically include additional one or more materials such as a filler, asolvent, a polymer, a surfactant, the residue of a crosslinker, a UVstabilizer, a thermal stabilizer, an antioxidant, a toughener, acolorant, a plasticizer, or a bleaching compound, or a combinationthereof.

The allyl compounds II and III and allyl adducts IV and V of theinvention are synthesized, in preferred embodiments, from biomass-basedfeedstocks. For example, the glycerol and 1,1,1-trimethylolpropaneketals of levulinic and pyruvic acid, and esters thereof, that form thePrecursors P1 and P2 are derivable or potentially derivable from biomasssources and do not require the use of petroleum based feedstocks. Thus,the current invention enables the synthesis of a biomass based set ofallyl compounds II and III and polymers, crosslinkers, and graftedmaterials made from them; allyl materials are well known to beindustrially useful in a wide variety of applications. In embodiments,at least 20% by weight of allyl compounds II and III and allyl adductsIV and V are biomass based. In other embodiments, between about 20% and90% by weight of the allyl compounds II and III and allyl adducts IV andV are biomass based. In other embodiments, between about 40% and 75% byweight of the allyl compounds II and III and allyl adducts IV and V arebiomass based. FIG. 11 shows a list of representative compounds of theinvention and their biomass content by weight. Additionally, the allylcompounds II and III and adducts thereof IV and V of the invention are,in some embodiments, biodegradable. Biodegradable allylic compounds areuseful for one or more applications, for example, in biodegradablecladding of cables and other items. In various embodiments, the allylcompounds II and III and adducts thereof IV and V of the inventionadvantageously supply the desirable properties of known allylicmonomers, polymers, and grafted materials and additionally supplybiodegradability thereof. Additionally, the allyl compounds II and IIIand adducts thereof IV and V are, in some embodiments, capable ofselective hydrolytic degradation at the ketal linkage. Ketal moietiesundergo rapid and quantitative hydrolytic degradation in the presence ofstrong mineral acid and water using mild temperatures and pressures toproduce a ketone and an alcohol. This selective degradation isaccomplished, in embodiments, in the presence of other functional groupssuch as esters, amides, alcohols, allyl groups, acrylates, carbonates,and ethers that remain intact. The selective degradation of the ketallinkage in the allyl adducts IV and V is employed in some embodiments toprovide additional functionality to the polymer, i.e. ketone or hydroxylgroups for further grafting reactions or compatibility and/or desireddifferences in hydrophilicity. Also, this chemical degradation may beadvantageous for lithography applications of the allyl adducts IV and Vin which a photo-acid generator (usually a strong acid) selectivelycleaves the labile ketal linkage of the allyl adducts IV and V togenerate hydroxyl groups or ketone groups for various applications. Anadditional advantage of selective degradation is that it enables, inembodiments, the breakdown of high molecular weight adducts to lowermolecular weight species for ease of disposal, recyclability, and/ordegradation by erosion or thermal means.

The Precursors P1 defined above are useful, in embodiments, for thesynthesis of glycidyl compounds II. Such embodiments include PrecursorP1 compounds wherein a is 0 or wherein a is between about 1 and 100.Such embodiments also include Precursor P1 compounds wherein β is 1; orwherein β is about 2 to 10. In embodiments, an epihalohydrin, such asepichlorohydrin, is used to functionalize a Precursor P1 compound byreacting with one or more hydroxyl moieties to form a glycidyl ether.The reaction between an alcohol and epihalohydrin to form a glycidylether, for example the reaction of the alcohol Bisphenol A withepichlorohydrin, is known in the literature. Any of the known literaturemethods of forming glycidyl ethers from epihalohydrins and alcohols areadvantageously employed in one or more embodiments of the invention toform one or more glycidyl compounds II. Andrews et al., U.S. Pat. No.5,420,312 disclose another technique usefully adapted to form glycidylcompounds II.

Precursor P2 compounds are useful, in embodiments, for the synthesis ofglycidyl compounds III. Such embodiments include Precursor P2 compoundswherein a is 0 or wherein a is between about 1 and 100. Such embodimentsalso include Precursor P2 compounds wherein β is 1_(;) or wherein β isabout 2 to 10. In some embodiments of Precursor P2 wherein R¹² ishydrogen and/or one or more carboxylic acid groups are present on R¹¹,glycidyl alcohol is used to synthesize glycidyl compounds III byesterification. In embodiments of Precursor P2 wherein R¹² is an alkylgroup and/or one or more carboxylic ester groups are present on R¹¹,glycidyl alcohol is used to synthesize glycidyl compounds III bytransesterification. Esterification and transesterification areaccomplished using any of the known techniques commonly employed in theliterature. For example, Chanda, M. and Roy, S., eds., PlasticsTechnology Handbook, 4^(th) ed., © 2007 Taylor & Francis Group, LLC, pp.4-114 to 4-116; and U.S. Pat. No. 5,536,855 describe some of the methodsthat are useful, in embodiments, to react one or more Precursors P2 withglycidyl alcohol.

In some embodiments where R¹² of Precursor P2 is hydrogen and/or one ormore carboxylic acid groups are present on R¹¹, epichlorohydrin isreacted directly with the carboxylic acid functionality to form thecorresponding glycidyl compound III; the reaction involves ring openingof the glycidyl moiety, followed by dehydrochlorination to re-form theoxirane ring similarly to the reaction of epichlorohydrin with analcohol. Such a reaction is carried out, in one or more embodiments, byemploying the techniques of Bukowska, et al., J. Chem. Tech. andBiotech., 74: 1145-1148 (1999); Otera et al., Synthesis (12), 1019-1020(1986); Dukes et al., U.S. Pat. No. 3,576,827; Henkel & Cie G.m.b.H.,British Patent No. GB 884,033; and Heer et al., German Patent Appl. No.DE 15945/70; or by other techniques found in the literature. One exampleof such a reaction scheme for the reaction of epichlorohydrin withPrecursor P2 wherein R² is —(CH₂)₂—, R³ is —CH₃, R⁴ is the residue ofglycerol, R¹¹ is —(CH₂)₄—, β is 2, a first α is 2 and a second α is 4,is shown in FIG. 3A. In still other embodiments where R¹² of PrecursorP2 is hydrogen and/or one or more carboxylic acid groups are present onR¹¹, carboxylate salts are formed using standard techniques; the saltsare then reacted with an epihalohydrin, such as epichlorohydrin, to formthe corresponding glycidyl compound III. In such embodiments, thetechniques employed by, for example, Maerker et al., J. Org. Chem. 26,2681-2688 (1961) are useful, among other techniques.

Another technique employed, in some embodiments, to provide glycidylfunctionality to one or more Precursors P1 and P2 of the invention is toreact an unsaturated site present on the molecule with a peroxide oranother oxidizing agent. For example, Au, U.S. Pat. No. 5,036,154,discloses a method whereby an ethylenically unsaturated ester group,such as an allyl ester, is reacted with a peroxide, such as benzoicperoxide, or a peracid, such as m-chloroperoxybenzoic acid, in thepresence of an alkali metal or alkaline earth metal salt of tungsticacid, phosphoric acid, and a phase transfer catalyst to give theepoxidized product of the unsaturated moiety. Such a technique is used,in embodiments, to form a glycidyl compound II or III of the inventionfrom the corresponding allyl compound II or III, the allyl compounds IIand III having been described above. An example of such a reaction isshown in FIG. 3B. Other techniques employed in the literature aresimilarly useful to obtain one or more epoxidized products of allylcompounds II and III of the invention. For example, esterification ortransesterification of a Precursors P2 of the invention with anunsaturated fatty acid ester is followed, in embodiments, by reactingthe unsaturated site with hydrogen peroxide, as is described by Du etal., J. Am. Org. Chem. Soc. 81(4) 477-480 (2004).

In a related reaction, the hydroxyl moieties of a Precursor P1 compoundmay be functionalized with isocyanate groups, then further reacted witha glycidyl alcohol to form oxiranyl compounds II. For example, in onesuch embodiment, a Precursor P1 having β of 2 and two hydroxyl moietiesis reacted with two equivalents of a diisocyanate to form two urethanegroups with terminal isocyanate moieties; in a subsequent reaction, theterminal isocyanates are reacted with glycidyl alcohol to give thecorresponding oxiranyl compound II. Suitable diisocyanates useful inreactions with the hydroxyl groups of the Precursors P1 include, withoutlimitation, those represented by formula OCN—Z—NCO and related compoundsas are described above.

In embodiments, the oxiranyl compounds II and glycidyl compounds III aresubsequently polymerized or grafted using standard techniques from theliterature to form oxiranyl adducts IV and V, respectively. The reactionof oxirane groups, for example with amines, amides, or anhydrides, iswidely known; of these, amines are the most commonly used compounds. Auseful summary of compounds and mechanisms of polymerizing oxiranegroups is found in Chanda, M. and Roy, S., eds., Plastics TechnologyHandbook, 4^(th) ed., © 2007 Taylor & Francis Group, LLC, pp. 4-116 to4-122. Any of the techniques employed or referenced therein are used, invarious embodiments, to react the oxirane or glycidyl compounds II andIII to form the corresponding linear, branched, or crosslinked polymericadducts IV and V as well as grafted compounds and polymers IV and VAmines useful in various embodiments as a reagent to polymerize oxiranylcompounds II and glycidyl compounds III include diamines and higherpolyamines. Suitable diamines and higher polyamines include hydrazine,ethane-1,2-diamine, 1,6-hexanediamine, but-2-ene-1,4-diamine, Metformin,butane-1,4-diamine, propane-1,2-diamine, piperazine,2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine,benzene-1,3-diamine, 2-methylbenzene-1,3-diamine,4-chlorobenzene-1,3-diamine, methanediamine,1,3,5-triazine-2,4,6-triamine, N-(2-aminoethyl)ethane-1,2-diamine,N-(6-aminohexyl)hexane-1,6-diamine,N,N′-bis(2-aminoethyl)ethane-1,2-diamine,N-[2-(3-aminopropylamino)ethyl]propane-1,3-diamine,4-(3,4-diaminophenyl)benzene-1,2-diamine, spermine(N,N′-bis(3-aminopropyl)butane-1,4-diamine), diethylene triamine,dipropylene triamine, dihexylene triamine,1,2,4-triazole-3,4,5-triamine, 2,4,5-triaminotoluene, melamine(1,3,5-triazine-2,4,6-triamine), benzene-1,3,5-triamine, triethylenetetramine, norspermine,N-[2-(3-aminopropylamino)ethyl]propane-1,3-diamine,4-(3,4-diaminophenyl)benzene-1,2-diamine, a polyethyleneimine, apolyoxyalkyleneamine having two or more amine groups, such as those soldunder the trade name JEFFAMINE®, (available from the Huntsman Corp. ofSalt Lake City, Utah), or any diamine or higher amine compound such asthose sold under the trade name ELASTAMINE® (available from the HuntsmanCorporation).

Formulations with oxiranyl compounds II and glycidyl compounds IIIinclude, in various embodiments, an amine (such as in a two-part glueformulation), one or more additional oxiranyl compounds to copolymerizewith the oxiranyl compounds II and glycidyl compounds III, a filler, asolvent, a polymer, a surfactant, a crosslinker, a UV stabilizer, athermal stabilizer, an antioxidant, a colorant, a plasticizer, or ableaching compound, or a combination thereof Additional “oxiranylcompounds” include compounds having two or more oxirane moieties thatare capable of copolymerization with oxiranyl compounds II and glycidylcompounds III. Examples of suitable additional oxiranyl compoundsinclude bisoxiranyl compounds such as2-(oxiran-2-ylmethoxymethyl)oxirane (diglycidyl ether)1,4-diglycidyloxybutane, bis(oxiran-2-ylmethyl)cyclohexane-1,2-dicarboxylate, 2-[6-(oxiran-2-yl)hexyl]oxirane,2-[2-(oxiran-2-yl)ethyl]oxirane,2-[2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxy]ethoxymethyl]oxirane,2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane (neopentylglycol diglycidyl ether), bis(2,3-epoxypropyl)adipate,2-[[4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane(diglycidyl adduct of Bisphenol A), 2-[2-(oxiran-2-yl)phenyl]oxirane,2-[[3-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane,N,N-bis(oxiran-2-ylmethyl)aniline, 1,4-bis(oxiran-2-ylmethyl)piperazine,diglycidyl isophthalate,[dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silyl]oxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane,and the like as well as trisoxiranyl and higher polyoxiranyl compounds,such as 4-(oxiran-2-ylmethoxy)-N,N-bis(oxiran-2-ylmethyl)aniline and2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane(pentaerythritol glycidyl ether).

In some embodiments, oxiranyl adducts IV and V are copolymers. Suchadducts arise where, for example, the oxiranyl compounds II and glycidylcompounds III are copolymerized with one or more additional oxiranylcompounds. Copolymers are also formed where, for example, more than onediamine is employed in the polymerization of the oxiranyl compounds IIand glycidyl compounds III. The properties and applications ofcopolymeric oxiranyl adducts IV and V, as well as the biomass contentthereof, are not particularly limited. Applications of oxiranyl adductsIV and V, including copolymers, and grafted adducts IV and V, arenumerous and broad in scope. Due to their high strength, variablecrosslink density, and variable chemical starting materials, oxiranylformulations, or epoxies, have found broad use in numerous applications.One of the most well known applications is in situ polymerization ofoxiranyl compounds deliverable as a two-part “glue”. Many of the mostcommon applications are set forth in Chanda, M. and Roy, S., eds.,Plastics Technology Handbook, 4^(th) ed., © 2007 Taylor & Francis Group,LLC, pp. 2-80 to 2-81, 7-26, and 4-124 to 4-125. The oxiranyl adducts IVand V, formed by curing and/or grafting the glycidyl and oxiranylcompounds II and III optionally in the presence of one or moreadditional oxiranyl compounds are, in various embodiments, useful in oneor more of these applications.

The oxiranyl compounds II and III and oxiranyl adducts IV and V of theinvention are synthesized, in preferred embodiments, from biomass-basedfeedstocks. For example, the glycerol and 1,1,1-trimethylolpropaneketals of levulinic and pyruvic acid, and esters thereof, that form thePrecursors P1 and P2 are derivable or potentially derivable from biomasssources and do not require the use of petroleum based feedstocks. Thus,the current invention enables the synthesis of a biomass based set ofoxiranyl compounds II and III and polymers, crosslinkers, and graftedmaterials made from them; oxiranyl materials are well known to beindustrially useful in a wide variety of applications. In embodiments,at least 20% by weight of the oxiranyl compounds II and III and oxiranyladducts IV and V are biomass based. In other embodiments, between about20% and 90% by weight of the oxiranyl compounds II and III and oxiranyladducts IV and V are biomass based. In other embodiments, between about40% and 75% by weight of the oxiranyl compounds II and III and oxiranyladducts IV and V are biomass based. FIG. 11 shows a list ofrepresentative compounds of the invention and their biomass content byweight. Additionally, the oxiranyl compounds II and III and adductsthereof IV and V of the invention are, in some embodiments,biodegradable. Biodegradable oxiranyl compounds are useful for one ormore applications, for example, in biodegradable adhesive formulations.In various embodiments, the oxiranyl compounds II and III and adductsthereof IV and V of the invention advantageously supply the desirableproperties of known oxiranyl monomers, polymers, and grafted materialsand additionally supply biodegradability thereof. Additionally, theoxiranyl compounds II and III and adducts thereof IV and V are, in someembodiments, capable of selective hydrolytic degradation at the ketallinkage. Ketal moieties undergo rapid and quantitative hydrolyticdegradation in the presence of strong mineral acid and water using mildtemperatures and pressures to produce a ketone and an alcohol. Thisselective degradation is accomplished, in embodiments, in the presenceof other functional groups such as esters, amides, alcohols, allylgroups, acrylates, carbonates, and ethers that remain intact. Theselective degradation of the ketal linkage in the oxiranyl adducts IVand V is employed in some embodiments to provide additionalfunctionality to the polymer, i.e. ketone or hydroxyl groups for furthergrafting reactions or compatibility and/or desired differences inhydrophilicity. Also, this chemical degradation is advantageous in someembodiments for lithography applications of the oxiranyl adducts IV andV, wherein a photo-acid generator (usually a strong acid) selectivelycleaves the labile ketal linkage of the oxiranyl adducts IV and V togenerate reactive hydroxyl groups or ketone groups for variousapplications. An additional advantage of selective degradation is thatit enables, in embodiments, the breakdown of high molecular weightadducts to lower molecular weight species for ease of disposal,recyclability, and/or degradation by erosion or thermal means.

The polycarbonates, acrylate and alkacrylate adducts, allyl adducts, andoxiranyl and glycidyl adducts IV and V are useful in a wide variety ofindustrially useful and significant applications. Various adducts IV andV of the invention are, in embodiments, used in blends, optionallyobtained by reactive extrusion. Blends include those of variouspolymers, for example various species of the polycarbonates, acrylicpolymers, allyl polymers, and oxiranyl polymers of the invention as wellas blends with such polymers as aliphatic/aromatic copolyesters, as forexample polybutylene terephthalate adipate (PBTA), polybutyleneterephthalate succinate (PBTS), and polybutylene terephthalate glutarate(PBTG); biodegradable polyesters such as polylactic acid,poly-E-caprolactone, polyhydroxybutyrates such aspoly-3-hydroxybutyrates, poly-4-hydroxybutyrates andpolyhydroxybutyrate-valerate, polyhydroxybutyrate-propanoate,polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate,polyhydroxybutyrate-dodecanoate, polyhydroxy-butyrate-hexadecanoate,polyhydroxybutyrate-octadecanoate, and polyalkylene succinates and theircopolymers with adipic acid, lactic acid or lactide and caprolactone andtheir combinations, and the like; polystyrene and copolymers thereof;polyurethanes; polycarbonates; polyamides such as Nylon 6 and Nylon 6,6;polyolefins such as polyethylene, polypropylene, and copolymers thereof;or any other industrially useful polymeric compounds. Blends alsoinclude, in some embodiments, composites with gelatinized, destructedand/or complexed starch, natural starch, flours, and other materials ofnatural, vegetable or inorganic origin. The adducts IV and V of theinvention are, in some embodiments, blended with polymers of naturalorigin, such as starch, cellulose, chitosan, alginates, natural rubbersor natural fibers (such as for example jute, kenaf, hemp). The starchesand celluloses can be modified, such as starch or cellulose esters witha degree of substitution of between 0.2 and 2.5, hydroxypropylatedstarches, or modified starches with fatty chains, among others.

The adducts IV and V, and blends of thereof, possess properties andvalues of viscosity that render them suitable for use, by appropriatelyadjusting the molecular weight, in numerous practical applications, suchas films, injection-molded products, extrusion coated products, fibers,foams, thermoformed products, extruded profiles and sheets, extrusionblow molding, injection blow molding, rotomolding, stretch blow moldingand the like.

In the case of films, production technologies like film blowing,casting, and coextrusion can be used. Moreover such films can be subjectto monoaxial or biaxial orientation in line or after film production. Itis also possible that the stretching is obtained in presence of anhighly filled material with inorganic fillers. In such a case, thestretching can generate micropores and the so obtained film can besuitable for hygiene applications. The adducts IV and V are suitable forthe production of films. A “film” is defined, for the purposes of theinvention, as a sheet type material that is flexible to e.g. bending andis between about 1 μm to 5 mm thick. Films employing the adducts IV andV are, in embodiments, one-directional or two-directional, single layeror multilayer, and employ an adduct IV or V as a single component or ina blend with other materials, as described above. The films are usefulfor various applications including agricultural mulching films;printable films for graphics or text; cling films (extensible films) forfoodstuffs, films for bales in the agricultural sector and for wrappingof refuse; shrink films such as for example for pallets, mineral water,six pack rings, and so on; bags and liners such as for collection ofrefuse, holding foodstuffs, gathering mowed grass and yard waste, andthe like; thermoformed single-layer and multilayer packaging forfoodstuffs, such as for example containers for milk, yogurt, meat,beverages, etc.; and in multilayer laminates with layers of paper,plastic materials, aluminum, metalized films for a wide variety ofapplications.

The adducts IV and V are also useful for coatings that form a layer ontop of a film, an article, and the like. Coatings of the invention areapplied, in embodiments, by extrusion coating, die coating, slotcoating, brush coating, spray coating, or any other generally knowntechnique employed in the coating industry. Coatings employing adductsIV and V are useful as protective coatings, paint components, adhesivesor glues, barrier layers, and the like. The coatings of the inventionare applied, in embodiments, with or without additional solvent(s), suchas coalescing solvents, and with our without additives such astougheners, plasticizers, surfactants, fillers, UV blocking agents,thermal stabilizers, antioxidants, antibacterial agents, colorants,fillers, and the like. The coatings of the invention are, in someembodiments, crosslinked after application.

Adducts IV and V are also useful in forming articles. An “article”, asdefined for the purposes of the invention, includes objects that are berigid or flexible; that exist as standalone objects or as part of anassembly or laminate; and that include adducts IV or a blend thereofwith one or more additional materials. Some examples of useful articlesthat include adducts IV are punnets for foodstuffs, I-beams forconstruction, casings for e.g. pens, computer screens, and the like;parts for automobile construction, table tops, and the like; decorativeitems such as lamp parts, jewelry, vases, architectural features, andthe like; children's toys; drink bottles; and many other articles. Theinvention is not particularly limited in terms of what articles may beformed employing the adducts IV and V of the invention.

Articles that can be formed include foamed articles. Foaming techniquesthat are generally known in the industry are used, in embodiments, toform foamed articles from the various adducts IV and V. Foamed articlesinclude both rigid and flexible foams. Some examples of useful foamedmaterials include cushions for automobile seats, interior or exteriorfurniture, and the like; foamed or foamable beads for the production ofpieces formed by sintering; foamed blocks made up of pre-foamedparticles; foamed sheets, thermoformed foamed sheets, and containersobtained therefrom for the packaging of foodstuffs.

Articles also include fibrous articles. Examples of fibrous articlesinclude standard scale fibers, microfibers, nanofibers, and compositefibers. Composite fibers have, in embodiments, a core constituted by arigid polymer such as PLA, PET, PTT, etc. and an external shell madewith one or more adducts IV; other composite fibers have various sectionconfigurations, e.g. from round to multilobed. Fibers also includeflaked fibers, woven and non-woven fabrics or spun-bonded orthermobonded fabrics for the sanitary sector, the hygiene sector, theagricultural sector, georemediation, landscaping and the clothingsector. Fibrous articles also include fiber-reinforced composites, whichinclude fibers, resins, and other components to form part of highstrength and rigidity. In such embodiments, the adducts IV and V make upall or a portion of the resin material used to impregnate the fibers.Carbon fiber is one example of a fiber that is useful in a fiberreinforced composite of the invention. In embodiments, compounds II andIII are used to impregnate the fiber, then polymerization and optionallygrafted is carried out in situ to form the composite adducts IV and V,respectively.

The allyl, oxiranyl and glycidyl compounds II and III are also useful,in one or more embodiments, as reactive diluents in a wide variety offormulations. Reactive diluents are compounds that are used, in someembodiments, to replace organic solvents in conventional high-VOC(volatile organic compound) coatings. Reactive diluents function likesolvents in adjusting coating viscosity for various applications.However, rather than evaporating like conventional solvents, reactivediluents participate in a chemical reaction with the coating componentsduring the curing process, and become incorporated into the curedcoating. As noted above, Precursors P2 include several species known tobe effective plasticizers in poly(vinyl chloride) formulations. Inembodiments, providing reactive endgroups onto these or other Precursorspecies P1 and P2 enables the compounds to be used as reactive diluentsin a formulation. Many coating applications feature reactive diluents tofacilitate coating viscosity, leveling, and the like, followed byreactions to incorporate the diluents into the polymeric networksubsequently formed.

The following Examples further elucidate and describe the compounds ofthe invention without limiting the scope thereof.

EXPERIMENTAL SECTION EXAMPLE 1

A 3-neck round bottom flask (rbf) was charged with 54.58 gm (0.25 moles)of ethyl 4-(2-hydroxymethyl-1,4-dioxolan-5-yl) pentanoate (“EtLGK”, madeaccording to the procedure of PCT Application No. WO 2009/048874). Therbf was equipped with 2 rubber septa, a thermocouple fitted using anadapter and Teflon coated magnetic spindle for stirring. Nitrogen purgewas started in the rbf and the stirrer was set at 400 rpm. Then 40.44 mL(0.5 moles) of pyridine (obtained from the Sigma-Aldrich Company of St.Louis, Mo.) was carefully added to the rbf using a 60 mL syringe. Therbf was immersed in an ice bath to cool the reaction mixture. When thetemperature of the mixture reached 0° C. (0.5° C. actual temperature),36.64 mL (0.375 moles) of methacryloyl chloride (obtained from the FlukaChemical Corporation of Milwaukee, Wis.) was slowly added to the rbfusing a 60 mL syringe. The reaction temperature was maintained below 25°C. by controlling the rate of addition of methacryloyl chloride. About20 minutes after completing the addition, the ice bath was removed andthe reaction mixture was allowed to warm to room temperature. Thereaction mixture was stirred at ambient temperature for another 3 hours.A white precipitate was observed to form during the 3 hours.

The white precipitate was dissolved in a mixture of 50 mL water and 50mL 0.1 N NaOH. The aqueous phase was then extracted with CH₂Cl₂ (3×100mL) and the resulting organic phase was washed with a saturated solutionof NaCl (1×50 mL) and dried using Na₂SO₄. Then 7.0 mg (3.39×10⁻⁵ moles)of 2,6-di-tert-butylphenol (obtained from the Sigma-Aldrich Company ofSt. Louis, Mo.) was added to the solution before removing the CH₂Cl₂ andpyridine by rotary evaporation. The final product was pale yellowliquid, which was analyzed by GC-MS and ¹HNMR. GC-MS data: 96.7% of themethacrylyl adduct of EtLGK, 3.3% crotonyl chloride.

EXAMPLE 2

A 20 mL scintillation vial was charged with 1.0 gm of the finalmethacrylate product of Example 1. Then 50 mg (5 wt %) AIBN (obtainedfrom the Sigma-Aldrich Company of St. Louis, Mo.) was added. The vialwas capped with a rubber septum. The reaction mixture was deoxygenatedby alternately pulling vacuum and back filling with nitrogen threetimes. The vial was placed in an oil bath heated to 70° C. The vialremained immersed in the oil bath for about 2 hours, then was removedand allowed to cool to ambient temperature. Then 10 mL of CH₂Cl₂ wasadded to the polymer and the contents of the vial were stirred overnightusing a Teflon coated magnetic spindle at 220 rpm. An undissolved solidproduct was filtered from the contents of the vial and washed withCH₂Cl₂ (2×10 mL). The washed product was dried overnight in a vacuumoven set to 120° C. at a pressure of about 300 millitorr. The whitetransparent product turned slightly yellow after drying in the oven. Theproduct was analyzed by DSC and was found to have a glass transitiontemperature (T_(g)) of 17.95° C. The DSC is shown in FIG. 4.

EXAMPLE 3

A 3-neck roundbottom flask (rbf) was charged with 43.66 gm (0.20 moles)EtLGK. The rbf was equipped with 2 rubber septa and a thermocouplefitted using an adapter. Nitrogen purge was started and was maintainedthroughout the course of the reaction. Then 32.35 mL (0.4 moles) ofpyridine (obtained from the Sigma-Aldrich Company of St. Louis, Mo.) wasadded using a 60 mL syringe. The rbf was immersed in an ice bath to coolthe reaction mixture to 0° C. Then 31.86 mL (0.3 moles) ofallylchloroformate (obtained from Acros Organics of Geel, Belgium) wasslowly added to the reaction mixture using a 60 mL syringe. Thetemperature of the reaction mixture was maintained below 25° C. bycontrolling the rate of addition of the allylchloroformate. After theaddition was completed, the contents of the flask were stirred in theice bath for an additional 20 minutes. Then the reaction mixture wasthen allowed to warm to ambient temperature and stirred for another 3hours. A white precipitated was observed in the rbf; the precipitate wasfiltered from the remainder of the flask contents using a Milliporefilter (0.45 μm HNWP, Millipore, Ireland). The liquid contents werewashed with 20 mL of 0.1 N NaOH, followed by 20 mL water, then and 20 mLof saturated NaCl solution. The washed product was dried with Na₂SO₄ andfiltered. The excess pyridine was removed using rotary evaporator. Thefinal product was a pale yellow liquid. The final product was analyzedby GC-MS, which showed 85% of the allylcarbonate adduct of EtLGK(rt=13.95-13.98 min) The GC-MS of the final product is shown in FIG. 5.

EXAMPLE 4

A single-neck round bottom flask (rbf) was charged with 5.0 gm (0.0165moles) of the final product of Example 3 and 30.0 mL of CHCl₃ (obtainedfrom Fisher Scientific of Waltham, Mass.), followed by addition of 3.8gm (0.0187 moles) 85% m-chloroperoxybenzoic acid (obtained from theSigma-Aldrich Company of St. Louis, Mo.). The rbf was equipped with acondenser and placed in an oil bath set at 63° C. The contents of theflask were refluxed for about 8.5 hrs. Then another 0.65 g (0.0032moles) of m-chloroperoxybenzoic acid was added to the flask and thecontents of the flask were refluxed for about 16 hours. A whiteprecipitated formed after the reaction was cooled to room temperature.The precipitate was filtered using Millipore filter and washed with 30mL CHCl₃. The liquid contents of the flask were washed with 1 N NaOH(2×10 mL), followed by water (10 mL) and sat. NaCl (10 mL), then driedwith Na₂SO₄ and filtered. The CHCl₃ was removed using rotovap. The finalproduct was a clear liquid that was analyzed by GC-MS. GC-MS data showeda yield of 73% of the oxiranylcarbonate adduct of EtLGK. The GC-MS ofthe final product is shown in FIG. 6.

EXAMPLE 5

A 2 liter, single neck round bottom flask was equipped with a stir barand charged with 873.90 g (6.07 mol) of ethyl levulinate (obtained fromLangfang Triple Well Chemicals Company, Ltd. Of Langfang City, HeBei,China), 407.5 g (3.04 mol) 1,1,1-trimethylolpropane (obtained from theSigma-Aldrich Company of St. Louis, Mo.) and 16.2 μl (0.304 mmol) of 98%sulfuric acid (obtained from the Sigma-Aldrich Company of St. Louis,Mo.). The flask was placed on a rotary evaporator with an oil bathtemperature of 75° C. and was subjected to a vacuum of between 10 and 20torr. The flask was rotated on the rotary evaporator for about 2.5 hoursand then the temperature of the oil bath was raised to 90° C. Thistemperature was maintained for about 1 hour and then the temperature wasincreased, again, to 100° C. and maintained for 1 hour 45 minutes. Thetemperature was then raised again to 110° C. and was maintained at thattemperature for about 10 minutes. For each step in temperature, thecontents of the reaction flask were observed to bubble and a liquid wasobserved to be condensing on the rotary evaporator. At the point thatthe bubbling stopped and liquid was observed to stop collecting on thecondenser, the next step in temperature was taken.

After the oil bath was maintained at 110° C. for about 10 minutes theflask was removed from the rotary evaporator and the contents of theflask allowed to cool to room temperature. A sample of the crudereaction product was removed from the flask and analyzed by GC. Theanalysis showed that the contents consisted of about 54.5% of thetrimethylolpropane ketal of ethyl levulinate (“EtLTMPK”), about 38.7%ethyl levulinate, about 4.9% trimethylolpropane, and approximately 1% ofunknown side reaction products.

Then 654.2 g of the crude reaction product was placed in a 1 liter roundbottom flask. Teflon boiling chips and a stir bar were added to theflask. The flask was equipped with a fractionation column, condenser,and vacuum/nitrogen inlet. A vacuum was applied to the flask, withstirring, until the pressure reached about 9 torr. A heating mantle wasapplied to the flask and the heat setting was set to 7.5 on a scale of10. After about 1 hour the temperature in the distillation column headwas observed to reach 74° C. Over the next 20 minutes the headtemperature was fluctuating between 74 and 85° C. and a liquid wasobserved to condense in the condensation column. Over the following 15minutes the temperature in the distillation head was observed to slowlyrise to 165° C. and a small fraction of the liquid distilling at 165° C.was collected. Then the vacuum was released and the contents of thereaction flask were allowed to cool to room temperature; a sample of thestripped crude reaction product was removed for GC analysis. The GCresults showed a yield of 89.7% EtLTMPK.

A 1 liter round bottom flask was charged with 401.90g of the strippedcrude reaction product and the flask placed on a rotary evaporator witha bump flask inserted between the 1 liter flask and the condenser columnof the rotary evaporator. The flask and bump flask were rotated in anoil bath set to 180° C. while a vacuum of about 4-8 torr was applied. Aclear liquid was observed to collect in the bump flask and periodicallythe vacuum on the rotary evaporator was released in order to empty thecontents of the bump flask into a clean, dry storage vessel. In this waythe entire batch of crude stripped reaction product was distilled andcombined.

The total yield of distilled, combined EtLTMPK was 69.9 mol % based ontheoretical. A sample of the distilled, combined EtLTMPK was subjectedto GC and TGA analysis. The GC showed 96.8% EtLTMPK.

A 3-neck roundbottom flask was charged with 26.06 gm (0.1 moles) of thedistilled, combined EtLTMPK and the flask was equipped with 2 rubbersepta and a thermocouple fitted using an adapter. Nitrogen purge wasstarted and was maintained throughout the course of the reaction. Then22.0 mL (0.2 moles) of pyridine (obtained from the Sigma-Aldrich Companyof St. Louis, Mo.) was added using a 30 mL syringe. The flask wasimmersed in an ice bath. Upon reaching a temperature of about 0° C. (0.5° C.), 15.0 mL (0.15 moles) of methacryloyl chloride (obtained from theFluka Chemical Corporation of Milwaukee, Wis.) was slowly added to theflask using an addition funnel The reaction temperature was maintainedbelow 25° C. by controlling the rate of addition of the methacryloylchloride. After completion of the addition, the flask was stirred in theice bath for about 20 minutes, then the flask was removed from the icebath and allowed to warm to ambient temperature. The reaction mixturewas stirred at ambient temperature for another 3 hours. At the end ofthe reaction period, a white precipitated was observed. The precipitatewas dissolved in 10 mL water and 10 mL 0.1 N NaOH. The aqueous phase wasextracted using CH₂Cl₂ (3×100 mL) and the resulting organic phase waswashed with once with 10 mL of a saturated NaCl solution, then driedusing Na₂SO₄ followed by filtration. Then 4.6 mg (2.22×10⁻⁵ moles) of2,6-di-tert-butylphenol (obtained from the Sigma-Aldrich Company of St.Louis, Mo.) was added to the solution before removing the CH₂Cl₂ andpyridine by rotary evaporation to yield the final product. The finalproduct was pale yellow liquid that was analyzed by GC-MS, which showeda yield of 92.4% of the methacryloyl adduct of EtLTMPK.

EXAMPLE 6

A 3-neck roundbottom flask (rbf) was charged with 26.14 gm (0.10 moles)EtLTMPK (intermediate product of Example 5) and the flask was equippedwith 2 rubber septa and a thermocouple fitted using an adapter. Nitrogenpurge was started and was maintained throughout the course of thereaction. Then 16.0 mL (0.2 moles) pyridine (obtained from theSigma-Aldrich Company of St. Louis, Mo.) was added using a 20 mLsyringe. The rbf was immersed in an ice bath to cool the reactionmixture to 0° C. (0.5° C.). Then 11.0 mL (0.15 moles) ofallylchloroformate (obtained from Acros Organics of Geel, Belgium) wasslowly added to the reaction mixture using an addition funnel Thereaction temperature was maintained below 25° C. by controlling the rateof addition of the allylchloroformate. After completion of the additionthe contents of the flask were stirred in the ice bath for an additional20 minutes, then the flask was removed from the ice bath and allowed towarm to ambient temperature. The contents of the flask were allowed tostir for an additional 3 hours. A white precipitated was observed toform during the reaction. The precipitate was filtered from the liquidcontents of the flask using a Millipore filter. The filtered reactionmixture was washed with 10 mL of 0.1 N NaOH, followed by 10 mL water and10 mL saturated NaCl solution, followed by drying with Na₂SO₄ andfiltration. The excess pyridine was removed using a rotary evaporator togive the final product. The final product was a pale yellow liquid whichwas analyzed by GC-MS and ¹H NMR. The GC-MS data showed 76.9% of theallylcarbonate adduct of EtLTMPK.

EXAMPLE 7

A 500 mL 3-neck round bottom flask was charged with 186.08 g (2.00 mol)glycerol (obtained from Acros Organics of Geel, Belgium) and 1045.88 g(8.04 mol) ethyl acetoacetate (obtained from the Sigma-Aldrich Companyof St. Louis, Mo.). The contents of the flask were observed to consistof a heterogeneous mixture of two liquid phases. The flask was equippedwith an overhead mechanical stirrer, a Dean-Stark separator with anoverhead condenser, and a thermocouple. The contents of the flask wereblanketed with a nitrogen stream and heated to 110° C. while stirring.Once the contents were at 90° C., 21.3 μL (2.0×10⁻⁴ moles) ofconcentrated sulfuric acid (obtained from the Sigma-Aldrich Company ofSt. Louis, Mo.) was added into the flask below the surface of thecontents by pipette. The contents of the flask began to bubble. Theinitial pressure in the flask was set to 300 Torr, and pressure was thenramped from 300 Torr to about 30 Torr over about 7 min. The contents ofthe flask were stirred for an additional 60 min at 25-30 Torr. Duringthis time, a distillate was collected in the Dean Stark separator. Thedistillate was observed to separate as it cooled. A sample of thereaction mixture was removed for GC-MS analysis. The GC trace showed noevidence of glycerol. Only excess ethyl acetoacetate and the ethylacetoacetate-glycerol ketal (EtAGK) were observed.

The EtAGK reaction product was poured into a beaker and neutralized byadding about 109g (10 wgt %) of basic alumina (obtained from theSigma-Aldrich Company of St. Louis, Mo.) and stirring the mixture forabout 30 minutes at room temperature. The solids were filtered from themixture using a fritted glass filter, fine grade. The liquids werevacuum distilled at between about 35 and 67 Torr using a 1 liter flask,fractionation column, condenser, and a cow with 3 catch flasks. A firstliquid was observed to distil at about 95° C., and this was collectedand analyzed by GC-MS and determined to be 100% ethyl acetoacetate. Asecond liquid was observed to distil at about 165° C. A very smallamount of residual material was left in the distillation flask at theend of the distillation. In the catch flask for the second liquid, bothliquid and an appreciable amount of a crystalline solid were observed.GC-MS showed that the second liquid was 99% EtAGK.

A 3-neck roundbottom flask (rbf) was charged with 30.62 gm (0.15 moles)EtAGK from and the flask was equipped with 2 rubber septa and athermocouple fitted using an adapter. Nitrogen purge was started and wasmaintained throughout the course of the reaction. Then 41.81 mL (0.3moles) of triethylamine (obtained from the Sigma-Aldrich Company of St.Louis, Mo.) was added using a 20 mL syringe. The rbf was immersed in anice bath to cool the reaction mixture to 0° C. (0.5° C.). Then 22.0 mL(0.225 moles) of methacryloyl chloride (obtained from the Fluka ChemicalCorporation of Milwaukee, Wis.) was slowly added to the reaction mixtureusing an addition funnel The reaction temperature was maintained below25° C. by controlling the rate of addition. After completion of theaddition the contents of the flask were stirred in the ice bath for anadditional 20 minutes, then the flask was removed from the ice bath andallowed to warm to ambient temperature. The contents of the flask wereallowed to stir for an additional 3 hours. A white precipitated wasobserved to form during the reaction. The precipitate was dissolved in10 mL water and 10 mL 0.1 N NaOH. The aqueous phase was extracted withCH₂Cl₂ (3×50 mL) and the resulting organic phase was washed with 10 mLof a saturated NaCl solution and dried using Na₂SO₄, followed byfiltration. Then 6.4 mg (3.1×10⁻⁵ moles) of 2,6-di-tert-butylphenol(obtained from the Sigma-Aldrich Company of St. Louis, Mo.) was added tothe solution before removing the CH₂Cl₂ and Et₃N by rotary evaporationto yield a final product. The final product was pale yellow liquid thatwas analyzed by GC-MS and ¹H NMR. GC-MS data showed 93.5% of themethacryloyl adduct of EtAGK.

EXAMPLE 8

A reactor with a 15 L jacketed glass kettle was equipped with mechanicalagitator, partial condenser attached to a circulating adjustabletemperature chiller, a second condenser between the partial condenserand the receiving flask, and 1 L receiving flask. The condensers wereboth equipped with circulation baths with temperature controllers. Thekettle was charged with 2.35 kg (16.31 moles) ethyl levulinate (obtainedfrom the Langfang Triple Well Chemicals Company, Ltd. of Langfang City,HeBei, China) and 2.50 kg (32.85 moles) 1,2-propanediol (obtained fromthe Brenntag North America, Inc. of Reading, Pa.). The agitator speedwas set to 50 rpm, the temperature of the partial condenser was set to80° C., the temperature of the second condenser was set to 7° C., andthe kettle temperature was set to 110° C. The pressure in the reactorwas reduced gradually to a target pressure of 10-15 Torr. A liquid wasobserved to collect in the receiver. After about 1 hour at the targetpressure and kettle temperature, the receiver was replaced with a fresh1 L receiving flask. The partial condenser temperature was set to 112°C. and the kettle temperature was set to 170° C.; these settings wereselected to allow excess propanediol and any unreacted ethyl levulinateto distill through the partial condenser and over to the secondcondenser, while the desired reaction product, the propanediol ketal ofethyl levulinate, was returned to the kettle by condensation in thepartial condenser. The pressure in the reactor was adjusted to 10-15Torr. When liquid stopped condensing in the receiver, a 5 L collectionflask was attached to the reactor and the remainder of the liquid in thereactor kettle was distilled as a crude distillate by setting thepartial condenser temperature to 110° C., kettle temperature to 170° C.,and adjusting pressure to 10-15 Torr. The distillation was stoppedbefore the reactor kettle was dry.

The crude distillate was analyzed by GC-FID and was determined to beabout 33.37% propylene glycol, 66.48% of the 1,2-propanediol ketal ofethyl levulinate (“EtLPK”), and 0.15% ethyl levulinate. About 1 L of thecrude distillate EtLPK was transferred to a 2 L separatory funnel Themixture was washed 2 times with 500 mL of brine solution and once with500 mL of deionized water. The organic layer was dried with magnesiumsulfate, filtered and analyzed for purity. Analysis of the washed anddried EtLPK product by GC-FID (calibrated to 100 ppm 1,2-propanediol)revealed no detectible propanediol and 0.14% ethyl levulinate.

EXAMPLE 9

The reaction to form the glycerol ketal of ethyl levulinate (“EtLGK”)was carried out according to the procedure of WO 2009/048874, Example 3,except that ethyl levulinate was obtained from the Langfang Triple WellChemicals Company, Ltd. of Langfang City, HeBei, China and was nottreated in any way prior to use; and glycerol was obtained from CargillInc. of Minnetonka, Minn. After synthesis was complete, EtLGK waspurified by distillation of ethyl levulinate from of the crude reactionmixture at 5 Torr and 70-75° C. Subsequently, the EtLGK product wasdistilled from the crude reaction mixture at 5 Torr and 150-155° C. Thefinal EtLGK product was determined to be 98.2% pure by GC-FID.

EXAMPLE 10

A 250 mL 3-neck round bottom flask was charged with 32.8 g (0.15 mol)EtLGK (synthesized according to the method of Example 9) and 91.0 g(0.45 mol) EtLPK (synthesized according to the method of Example 8). Theflask was equipped with a mechanical stirrer, thermocouple, a Dean-Starkapparatus with condenser, and an inlet and outlet for nitrogen. Thecontents of the flask were stirred under a vacuum of about 6 torr andheated to 110° C. using a heating mantle. The flask was back-filled withnitrogen, a sample was taken from the flask, and the water content inthe flask was measured to be 33 ppm by Karl Fischer titration. Then 9.7μL of a titanium tetra-isoproxide (obtained from the Sigma-AldrichCompany of St. Louis, Mo.) was added into the flask. Nitrogen purge wasmaintained and the contents of the flask were heated to 230° C. using aheating mantle. During the reaction, a liquid was observed to collect inthe Dean-Stark trap. After a maintaining the temperature of 230° C. forabout 2 hours the reaction mixture was cooled to 110° C., anddistillation of a second liquid was accomplished using reduced pressureof about 4 Torr. The reaction mixture was allowed to cool to ambienttemperature when no further distillate was collected.

After establishing atmospheric pressure in the flask, a sample wasremoved and analyzed by GPC. The composition as measured by GPC wasabout 48.6% of the 1:1 adduct of EtLGK : EtLPK, about 26.8% of the 2:1adduct of EtLGK : EtLPK, about 12.2% of the 3:1 adduct of EtLGK : EtLPK,about 8.2% of the 4:1 adduct of EtLGK : EtLPK, and about 4.3% total ofthe starting materials EtLGK and EtLPK.

EXAMPLE 11

A 3-neck round bottom flask (rbf) was charged with 51.04 gm (0.1 moles)of the LPK-LGK adduct mixture of Example 10. The rbf was equipped with athermocouple fitted using an adapter, a Dean-Stark fitted with acondenser, an adapter for nitrogen purge and Teflon coated magneticspindle for stirring. Nitrogen purge was started in the rbf and thestirrer was set at 300 rpm. Then 10.2 mL (0.15 moles) of allyl alcohol(obtained from the Sigma-Aldrich Company of St. Louis, Mo.) wascarefully added to the rbf using a 10.0 mL syringe. The rbf was heatedusing a heating mantle connected to a temperature controller to 70° C.When the temperature of the mixture reached 70° C., 0.299 gm (0.0044) ofsodium ethoxide (obtained from the Fluka Chemical Corporation ofMilwaukee, Wis.) was added to the rbf. The set point on the temperaturecontroller was increased to 90° C. Once the reaction mixture reaches 85°C. volatiles generated is collected in the Dean-Stark adapter. Thereaction mixture was stopped once the volatiles stopped collecting inthe Dean-Stark (5.0 mL). The reaction was cooled and analyzed by GPC and¹HNMR. Final product was a dark brown viscous liquid. GPC data: 15.8%oligomerallylester (n=4), 13.4% tetramer allyl ester (n=3), 20.1% trimerallyl ester (n=2), 27.5% mono allylester, and 23.1% EtLPK.

EXAMPLE 12

A 250 ml 4-neck round bottom flask was charged with 43.62 g (0.2 mol)EtLGK synthesized according to the method of Example 9 and 80.90 g (0.4mol) of diethyl adipate (obtained from the Sigma Aldrich Company of St.Louis, Mo., and distilled prior to use). The flask was equipped with amechanical stirrer, thermocouple, and an inlet for nitrogen and outletto a bubbler. The contents of the flask were heated to 60° C. on aheating mantle, and purged with nitrogen to dry the reactor contentsuntil the water concentration of the flask contents was less than 100ppm as determined by Karl Fischer titration. The flask was then equippedwith a Dean Stark trap, condenser, and a firestone valve which allowedfor either vacuum or nitrogen to enter the system. Next 12.02 μl oftitanium tetra-isopropoxide (obtained from Acros Organics of Geel,Belgium) was added to the reaction flask via a microliter syringe. Thecontents of the flask were then heated to 110° C. Then the reaction wasdegassed by applying a vacuum of 3 to 5 Torr to the reaction flask for 5min. While under vacuum, the glassware was flame-dried to eliminate anyadditional moisture in the system. After pulling vacuum, the reactionflask was back filled with nitrogen for 5 min. This process was repeatedthree times.

The contents of the flask were then heated to 230° C. under constantnitrogen purging. A liquid was observed to collect in the Dean Starktrap; the rate of collection was monitored to determine the rate ofconversion of the condensation reaction. After about 160 minutes ofcollecting liquid, the heat was shut off and the contents of the flaskwere allowed to cool to ambient temperature. The conversion hadreached >99% by measuring the amount of residual EtLGK in the reactor byGC-FID. The reaction mixture was subsequently distilled under vacuum toremove volatiles until the level of EtLGK and diethyl adipate in thefinal product was below 1%. The final reaction composition, asdetermined by GPC, was approximately 45% of the 1:1 adduct ofadipate:LGK, 27% 1:2 adipate:LGK adduct, 27% 1:3 adipate:LGK and higheroligomers, and 1% combined total of diethyl adipate and EtLGK.

EXAMPLE 13

A 3-neck round bottom flask (rbf) was charged with 57.55 gm (0.13 moles)of the product of Example 12. The rbf was equipped with a thermocouplefitted using an adapter, a Dean-Stark fitted with a condenser, anadapter for nitrogen purge and Teflon coated magnetic spindle forstirring. Nitrogen purge was started in the rbf and the stirrer was setat 500 rpm. Then 31.82 mL (0.47 moles) of allyl alcohol (obtained fromthe Sigma-Aldrich Company of St. Louis, Mo.) was carefully added to therbf using a 30 mL syringe. The rbf was heated using a heating mantleconnected to a temperature controller to 70° C. When the temperature ofthe mixture reached 70° C., 0.424 gm (0.0062 moles) of sodium ethoxide(obtained from the Fluka Chemical Corporation of Milwaukee, Wis.) wasadded to the rbf. The set point on the temperature controller wasincreased to 90° C. Once the reaction mixture reaches 85° C. volatilesgenerated is collected in the Dean-Stark adapter. The reaction mixturewas stopped once the volatiles stopped collecting in the Dean-Stark(17.5 mL). The reaction was cooled and analyzed by GPC. The sodiumethoxide was neutralized by adding 4.1 gm (0.031 moles) of ammoniumsulfate to the reaction mixture and heating it to 100° C. under 80-90torr vacuum for about 1 hour. Then the pH of the reaction mixture wasmeasured (pH=8.9). The solids were removed by filtration using aMillipore filter (0.45 μm, HNWP Millipore, Ireland). Volatiles weredistilled out using a short path distillation column under 0.5 torrvacuum while heating the flask in an oil bath set to 220° C. The finalproduct was a dark brown viscous liquid that was analyzed by GPC. GPCdata: 14.4% oligomeric diallyl ester (n=3), 21.6% trimer diallyl ester(n=2), 43.9% mono diallyl ester (n=1), and 0.96% LGK allyl ester.

EXAMPLE 14

A 3-neck round bottom flask (rbf) was charged with 36.86 gm (0.182moles) of EtLPK. The rbf was equipped with a thermocouple fitted usingan adapter, a Dean-Stark fitted with a condenser, an adapter fornitrogen purge and Teflon coated magnetic spindle for stirring. Nitrogenpurge was started in the rbf and the stirrer was set at 300 rpm. Then15.5 mL (0.273 moles) of allyl alcohol (obtained from the Sigma-AldrichCompany of St. Louis, Mo.) was carefully added to the rbf using a 20 mLsyringe. The rbf was heated using a heating mantle connected to atemperature controller to 70° C. When the temperature of the mixturereached 70° C., 0.261 gm (0.0038 moles) of sodium ethoxide (obtainedfrom the Fluka Chemical Corporation of Milwaukee, Wis.) was added to therbf. The set point on the temperature controller was increased to 90° C.Once the reaction mixture reaches 85° C. volatiles generated werecollected in the Dean-Stark adapter. The reaction mixture was stoppedonce the volatiles stopped collecting in the Dean-Stark (4.0 mL). Sodiumethoxide (was neutralized by adding 2.53 gm (0.019 moles) ammoniumsulfate to the reaction mixture and heating it to 60° C. under 80-90torr vacuum for 1 hour. The solids were then removed by filtration usinga Millipore filter (0.45 μm, HNWP Millipore, Ireland). The reaction wascooled and analyzed by GC-MS. Final product was a light yellow liquid.GC-MS data: 60% of the allyl ester.

EXAMPLE 15

A 3-neck round bottom flask (rbf) was charged with 13.78 gm (0.04 moles)of product of Example 6. The rbf was equipped with a thermocouple fittedusing an adapter, a Dean-Stark fitted with a condenser, an adapter fornitrogen purge and Teflon coated magnetic spindle for stirring. Nitrogenpurge was started in the rbf and the stirrer was set at 400 rpm. Then4.08 mL (0.06 moles) of allyl alcohol (obtained from the Sigma-AldrichCompany of St. Louis, Mo.) was carefully added to the rbf using a 5.0 mLsyringe. The rbf was heated using an oil bath which was heated to 100°C. 0.086 gm (0.0013 moles) of sodium ethoxide (obtained from the FlukaChemical Corporation of Milwaukee, Wis.) was added to the rbf. Novolatiles were generated. The oil bath was heated to 107° C. and after30 mins the reaction mixture was subjected to full vacuum, around 50torr. The reaction mixture started boiling vigorously, so that vacuumpump was switched off and the rbf was back filled with nitrogen. Thereaction mixture was stopped once the volatiles had stopped collecting(<1.0 mL). The reaction was cooled and analyzed by GC-MS. GC-MS showed amixture of products. The yield of the diallyl derivative was 9.0%. Therewas also 22.25% of the allyl compound structure shown below:

EXAMPLE 16

A 3-neck round bottom flask (rbf) was charged with 20.42 gm (0.1 moles)of EtAGK synthesized as in Example 7. The rbf was equipped with athermocouple fitted using an adapter, a Dean-Stark fitted with acondenser, an adapter for nitrogen purge and Teflon coated magneticspindle for stirring. Nitrogen purge was started in the rbf and thestirrer was set at 300 rpm. Then 17.0 mL (0.25 moles) of allyl alcohol(obtained from the Sigma-Aldrich Company of St. Louis, Mo.) wascarefully added to the rbf using a 5.0 mL syringe. The rbf was heatedusing an oil bath which was heated to 100° C. 0.175 gm (0.0026 moles) ofsodium ethoxide (obtained from the Fluka Chemical Corporation ofMilwaukee, Wis.) was added to the rbf. The reaction mixture was stoppedonce the volatiles had stopped collecting (5.5 mL). The reaction wascooled and analyzed by GC-MS. GC-MS data showed 60% of the allyl ester.

EXAMPLE 17

A single-neck round bottom flask (rbf) was charged with 1.01 gm (0.0046moles) of the product of Example 14 and 10.0 mL of acetonitrile(obtained from Fisher Scientific of Waltham, Mass.), followed byaddition of 1.5 gm (0.0087 moles) 85% m-chloroperoxybenzoic acid(obtained from the Sigma-Aldrich Company of St. Louis, Mo.). The rbf wasequipped with a condenser and placed in an oil bath set at 85° C. Thecontents of the flask were refluxed for about 9 hrs. A whiteprecipitated formed after the reaction was cooled to room temperature.The precipitate was filtered using Millipore filter (0.45 μm, HNWPMillipore, Ireland) and washed with 10 mL acetonitrile; the wash wasadded to the liquids. Acetonitrile was stripped from the flask by rotaryevaporation. The final product was a clear liquid that was analyzed byGC-MS. Yield by GC-MS was 32% of the glycidyl ester.

EXAMPLE 18

A 3-neck round bottom flask (rbf) was charged with 43.66 gm (0.15 moles)of EtLGK, synthesized according to the procedure of Example 9. The rbfwas equipped with a thermocouple fitted using an adapter, a condenser,an adapter for nitrogen purge and Teflon coated magnetic spindle forstirring. Nitrogen purge was started in the rbf and the stirrer was setat 400 rpm. The rbf was heated to 70° C. using a heating mantle and theEtLGK was dried under vacuum (5-7 torr) for about 1 hour. Then 25.4 mL(0.3 moles) of allyl bromide (obtained from the Sigma-Aldrich Company ofSt. Louis, Mo.) was added to the rbf with stirring, using a 30.0 mLsyringe. After about 15 minutes of stirring under nitrogen, 41.46 gm(0.3 moles) of K₂CO₃ (obtained from Acros Organics of Geel, Belgium) wasadded. The temperature of the reaction mixture was increased to 125° C.and were maintained at this temperature with stirring for about 22hours. The contents of the flask were allowed to cool to ambienttemperature. A white precipitate was observed in the flask. Theprecipitate was filtered using a Millipore filter (0.45 μm, HNWPMillipore, Ireland) and the liquid remainder was analyzed by GC-MS,which showed 27.5% yield of the allyl ether EtLGK.

EXAMPLE 19

A 3-neck round bottom flask (rbf) was charged with 50.71 gm (0.11 moles)of the product of Example 12. The rbf was equipped with a thermocouplefitted using an adapter, a Dean-Stark trap with a condenser, an adapterfor nitrogen purge and overhead mechanical stirrer with a stir shaftconnected using an adapter and Teflon sleeve. Nitrogen purge andstirring were started in the rbf. The rbf was heated to 70° C. using aheating mantle, and vacuum of about 7-9 torr was applied with stirring,while the temperature was maintained for about 1 hour. Then 12.2 mL (0.1moles) of diethyl carbonate (obtained from the Sigma-Aldrich Company ofSt. Louis, Mo.) was added to the reaction mixture using a 20 mL syringe.After about 10 minutes, 0.04 gm (0.0055 moles) of solid NaOEt (obtainedfrom the Fluka Chemical Corporation of Milwaukee, Wis.) was added to theflask. The temperature of the contents of the flask was increased to150° C. and was maintained at that temperature while a liquid wasobserved to collect in the Dean-Stark trap. The reaction mixture wasremoved from the heating mantle and allowed to cool to ambienttemperature when liquid collection stopped. About 3.0 mL total liquidwas collected. The contents of the flask were analyzed by GPC and ¹HNMR. The product was a dark brown viscous liquid. GPC data (PS std):Mw=1364 (PDI=1.63), 2.88% EtLGK; Tg (DSC)=−41.3° C. The GPC is shown inFIG. 7 and the DSC is shown in FIG. 8.

EXAMPLE 20

A 3-neck round bottom flask (rbf) was charged with 6.0 gm (0.0133 moles)of the product of Example 13 and 36.0 mL of CHCl₃ followed by additionof 9.5 gm (0.047 moles) 85% m-chloroperoxybenzoic acid (obtained fromthe Sigma-Aldrich Company of St. Louis, Mo.). The rbf was equipped witha condenser, thermocouple fitted with an adapter and a glass stopper.The rbf was heated to reflux using a heating mantle. Reflux wascontinued for about 16 hours, then the contents of the flask wereallowed to cool to ambient temperature. A white precipitate formed afterthe reaction was cooled. The precipitate was removed by filtration andwashed with 35 mL CHCl₃. The liquid contents of the flask were washedtwice with 10 mL aliquots of 1 N NaOH followed by 10 mL water and the 10mL saturated NaCl solution. The washed product was dried with Na₂SO₄ andfiltered. The CHCl₃ was removed using rotary evaporation. The finalproduct was a clear liquid that was analyzed by GPC and ¹H NMR. Yield byGPC was 40% of diepoxide of the product of Example 13.

EXAMPLE 21

A 1-neck round bottom flask (rbf) was charged with 3.64 gm (0.0081moles) of the diepoxide product of Example 20 and 1.41 gm (0.012 moles)1,6-hexamethylenediamine (obtained from the Sigma-Aldrich Company of St.Louis, Mo., distilled prior to use). The rbf was equipped with magneticstir bar and nitrogen purge and was heated using a temperaturecontrolled oil bath 140° C. Nitrogen purge was started in the rbf andthe magnetic stirrer was set at 400 rpm. The contents of the flask wereheated immersed in the oil bath until the temperature reached 140° C.,then the flask was removed from the oil bath and the contents allowed tocool to ambient temperature. The contents of the flask were analyzed byDSC and TGA. Final product was a dark brown viscous liquid. Tg(DSC)=−20.3° C.

EXAMPLE 22

A 250-mL disposable cup was charged with 9.98 gm of the product ofExample 19. Using a microliter syringe, 23 μl (0.25 parts per 100 partspolyol) of dibutyltin dilaurate (98%, obtained from Pfaltz and Bauer,Inc. of Waterbury, Conn.) was added to the cup. Using a microlitersyringe, 24 μl (0.25 parts per 100 parts polyol) of triethylenediamine(DABCO 33LV, obtained from Air Products and Chemicals, Inc. ofAllentown, Pa.) was added to the cup and hand-mixed with a tonguedepressor until homogeneous. Then 2.08 gm (103% isocyanate index)toluenediisocyanate (Mondor TD-80, obtained from Bayer MaterialScienceof Hong Kong, P.R. China) was weighed into the cup and hand-mixed untilhomogeneous. The cup was allowed to sit in a fume hood overnight. Thesample was found to be soluble in methylene chloride and insoluble inhexane. The product was analyzed by DSC; Tg=9.33° C. The DSC of theproduct is shown in FIG. 9.

EXAMPLE 23

A 250-mL disposable cup was charged with 9.98 gm Example 19 using amicroliter syringe, 23 μl (0.25 parts per 100 parts polyol) ofdibutyltin dilaurate (98%, obtained from Pfaltz and Bauer, Inc. ofWaterbury, Conn.) was added to the cup. Again using a micro syringe, 24μl (0.25 parts per 100 parts polyol) of triethylenediamine catalyst(DABCO 33LV, obtained from Air Products and Chemicals, Inc. ofAllentown, Pa.) was added to the cup and hand-mixed with a tonguedepressor until homogeneous. 3.13 gm (103% isocyanate index) polymericMDI (PAPI 94, obtained from the Dow Chemical Company of Midland, Mich.)was weighed into the cup and hand-mixed until homogeneous. The cup wasallowed to sit in a fume hood overnight. The contents of the cup werefound to be slightly soluble in methylene chloride and insoluble inhexane. The contents of the cup were analyzed by DSC; Tg=9.49° C. TheDSC of the product is shown in FIG. 10.

The various embodiments described above are provided by way ofillustration only and should not be construed to limit the claimsattached hereto. The present invention may suitably comprise, consistof, or consist essentially of, any of the disclosed or recited elements.Thus, the invention illustratively disclosed herein can be suitablypracticed in the absence of any element which is not specificallydisclosed herein. Various modifications and changes will be recognizedthat may be made without following the example embodiments andapplications illustrated and described herein, and without departingfrom the true spirit and scope of the following claims.

1. A compound having the structure P2:

wherein R² is a covalent bond or a linear, branched, or cyclic alkyl,alkenyl, or alkynyl group having 1 to 18 carbon atoms, or an aryl oralkaryl group having between 7 and 36 carbon atoms; R³ is hydrogen,alkynyl, or a linear, branched, or cyclic alkyl or alkenyl group having1 to 18 carbon atoms, or an aryl or alkaryl group having from 7 to 36carbon atoms; R⁴ is silyl, silane, or siloxane, or a hydrocarbon grouphaving the formula

wherein a is 0 or 1 and R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independentlyhydrogen, alkynyl, a linear, branched, or cyclic alkyl group having 1 to18 carbon atoms, a linear or branched alkenyl group having 1 to 18carbon atoms, an aryl group, or an alkaryl group having from 7 to 18carbon atoms; R¹¹ is a monovalent, divalent, or multivalent linear,branched, or cyclic alkyl group having 1 to 36 carbon atoms, a linear orbranched alkenyl group having 1 to 36 carbon atoms, an aryl group, oralkaryl group having from 7 to 36 carbon atoms, or a ketal residuecomprising the structure

wherein R^(2′), R^(3′), and R^(4′) are as defined for R², R³, and R⁴respectively; R¹² is hydrogen or a linear or branched alkyl group havingbetween 1 and 8 carbons; α is an integer of 1 to about 100, and wherethere is more than one α, the values of α are the same or different; andβ is an integer of 1 to about
 10. 2. The compound of claim 1 wherein R¹¹further comprises one or more additional functional groups comprisinghalogen, tertiary amine, carbonate, ether, carboxylic acid, carboxylicester, carbonyl, urethane, imide, amide, or a combination thereof. 3.The compound of claim 1 wherein R² is —(CH₂)₂—, R³ is —CH₃, and R⁴ isthe residue of glycerol.
 4. The compound of claim 1 wherein R¹¹ is theresidue of a diacid, the diacid comprising oxalic acid, malonic acid,succinic acid, adipic acid, pimellic acid, suberic acid, dodecane-dioicacid, azelaic acid, a dimer acid, sebacic acid, or o-, m-, or p-phthalicacid.
 5. The compound of claim 4 wherein β is
 1. 6. The compound ofclaim 4 wherein β is
 2. 7. The compound of claim 2 wherein R¹¹ is theketal residue and R^(2′) is —(CH₂)₂—, R^(3′) is —CH₃, and R^(4′) is theresidue of 1,2-propanediol or 1,2-ethanediol.
 8. The compound of claim 7wherein one or more a is between about 1 and
 4. 9. A compound comprisingone or more repeat units IA, IB, or a combination thereof:

wherein R¹ is a divalent linear, branched, or cyclic alkyl group having1 to 36 carbon atoms, a linear or branched alkenyl group having 1 to 36carbon atoms, an aryl group, or an alkaryl group having from 7 to 36carbon atoms; R² is a covalent bond or a linear, branched, or cyclicalkyl group having 1 to 18 carbon atoms, a linear or branched alkenylgroup having 1 to 18 carbon atoms, an aryl group, or an alkaryl grouphaving from 7 to 18 carbon atoms; R³ is hydrogen, alkynyl, or a linear,branched, or cyclic alkyl group having 1 to 18 carbon atoms, a linear orbranched alkenyl group having 1 to 18 carbon atoms, an aryl group, or analkaryl group having from 7 to 18 carbon atoms; R⁴ is a group having theformula

wherein a is 0 or 1 and R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independentlyhydrogen, alkynyl, or linear, branched, or cyclic alkyl groups having 1to 18 carbon atoms, linear or branched alkenyl groups having 1 to 18carbon atoms, aryl groups, or alkaryl groups having from 7 to 18 carbonatoms; αand α′ are independently integers of 1 to about 100; and γ is aninteger of 1 to about 30 and γ is the same or different for repeat unitIA and repeat unit IB.
 10. The compound of claim 9 wherein R¹ furthercomprises one or more functional groups comprising halogen, tertiaryamine, hydroxyl, carbonate, carboxylic acid, carboxylic ester, ether,carbonyl, ketal, urethane, imide, amide, or a combination thereof. 11.The compound of claim 9 wherein compound IA, IB, or both furthercomprise hydroxyl functional endgroups.
 12. The compound of claim 9wherein one or more α, α′, or both are independently between 0 and about5.
 13. The compound of claim 9 wherein R² is —(CH₂)₂—, and R³ is —CH₃,and R⁴ is the residue of glycerol.
 14. The compound of claim 9 whereinabout 25% by weight or more of the compound is biomass based.
 15. Thecompound of claim 9 wherein between about 25% and 90% by weight of thecompound is biomass based.
 16. The compound of claim 9 wherein betweenabout 40% and 75% by weight of the compound is biomass based.
 17. Thecompound of claim 9 wherein the compound is biodegradable.
 18. Thecompound of claim 9 wherein one or more values of γ is between about 1and 10 and compound IA, compound IB, or both further comprise hydroxylfunctional endgroups.
 19. The compound of claim 9, wherein one or more γis between about 1 and 10 and compound IA, compound IB, or both furthercomprise one or more repeat units comprising a polyurethane moiety. 20.A formulation comprising a. one or more compounds of claim 9, and b. afiller, a solvent, a polymer, a surfactant, a crosslinker, a UVstabilizer, a thermal stabilizer, an antioxidant, a colorant, aplasticizer, or a bleaching compound, a fiber, or a combination of twoor more thereof.
 21. (canceled)
 22. An article comprising the compoundof claim 9, wherein the article comprises a container, a fiberreinforced composite part, a transparent windowpane, a film, a fiber, afoam, a coating, or a laminate.
 23. A formulation comprising a. one ormore compounds of claim 19, and b. a filler, a solvent, a polymer, asurfactant, a crosslinker, a UV stabilizer, a thermal stabilizer, acolorant, a plasticizer, or a bleaching compound, a fiber, or acombination of two or more thereof.
 24. A compound having structure II:

wherein R¹ is hydrogen or a monovalent, divalent, or multivalent linear,branched, or cyclic alkyl group having 1 to 36 carbon atoms, amonovalent, divalent, or multivalent linear or branched alkenyl grouphaving 1 to 36 carbon atoms, a monovalent, divalent, or multivalent arylgroup, or a monovalent, divalent, or multivalent alkaryl group having 7to 36 carbon atoms; R² is a covalent bond or a linear, branched, orcyclic alkyl group having 1 to 18 carbon atoms, a linear or branched,alkenyl group having 1 to 18 carbon atoms, an aryl group, or an alkarylgroup having 7 to 18 carbon atoms; R³ is hydrogen, alkynyl, or a linear,branched, or cyclic alkyl group having 1 to 18 carbon atoms, a linear orbranched, alkenyl group having 1 to 18 carbon atoms, an aryl group, oran alkaryl group having 7 to 18 carbon atoms; R⁴ is a group having theformula

wherein a is 0 or 1 and R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independentlyhydrogen, alkynyl, or a linear, branched, or cyclic alkyl group having 1to 18 carbon atoms, a linear or branched, alkenyl group having 1 to 18carbon atoms, an aryl group, or an alkaryl group having 7 to 18 carbonatoms; R¹³ is an acrylyl, alkacrylyl, oxiranyl, or allyl group, or alinear, branched, or cyclic alkyl, aryl, or alkaryl group comprising anacrylyl, alkacrylyl, oxiranyl, or allyl moiety; α is an integer of 1 toabout 100, and where there is more than one α, the values of α are thesame or different; and β is an integer of 1 to about
 10. 25. Thecompound of claim 24 wherein R¹, R¹³, or both further comprise one ormore halogen, tertiary amine, amide, carbonate, ether, ester, keto,ketal, or urethane functionalities.
 26. The compound of claim 24 whereinβ is 1 or
 2. 27. The compound of claim 24 wherein R² is —(CH₂)₂—, and R³is —CH₃, and R⁴ is the residue of glycerol.
 28. The compound of claim 24wherein about 20% by weight or more of the compound is biomass based.29. The compound of claim 24 wherein between about 20% and 90% by weightof the compound is biomass based.
 30. The compound of claim 24 whereinbetween about 40% and 75% by weight of the compound is biomass based.31. The compound of claim 24 wherein the compound is biodegradable. 32.A formulation comprising a. a compound of claim 24, and b. a freeradical initiator, an alcohol, an amine, a vinyl compound, an oxiranylcompound, a chain transfer agent, a filler, a solvent, a polymer, asurfactant, a UV stabilizer, a thermal stabilizer, an antioxidant, acolorant, a plasticizer, a fiber, or a bleaching compound, or acombination of two or more thereof.
 33. The formulation of claim 32wherein the vinyl compound comprises acrylic acid, methacrylic acid, analkyl acrylate, an alkyl methacrylate, and acrylate salt, a methacrylatesalt, vinyl acetate, acrylamide, methacrylamide, N-hydroxymethylacrylamide, methacryloxyethyl phosphate, acrylonitrile,methacrylonitrile, 2-acrylamido-2-methylpropanesulfonic acid or a saltthereof, maleic acid, maleic anhydride, an alkyl maleate, a maleatesalt, glycidyl methacrylate, hydroxyethyl methacrylate, hydroxypropylmethacrylate, chloro acrylic acid, an alkyl chloro acrylate; ethylene,propylene, an α-olefin such as α-hexene or α-octene, vinyl toluene,N—N-vinyl pyrrolidone, divinyl benzene, styrene, α-methyl styrene,t-butyl styrene, chlorostyrene, or a monohydric or polyhydric alcoholester of acrylic and alkylacrylic acid such as ethylene glycoldiacrylate, 1,6 hexane diol diacrylate, neopentyl glycol diacrylate, 1,3butylene dimethacrylate, ethylene glycol diacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate, or pentaerythritoltetraacrylate; prop-2-enyl heptanoate, prop-2-enoxybenzene, prop-2-enylacetate, allyl vinyl ether, allyl methyl ether, bisallyl ether, allyladipate, diallyl carbonate, pentaerythritol tetraallyl ether,1-N,4-N-bis(prop-2-enyl)benzene-1,4-dicarboxamide, or a combinationthereof.
 34. The formulation of claim 32 wherein the oxiranyl compoundis2-[[4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane.35. (canceled)
 36. A compound having structure III:

wherein R² is a covalent bond or a linear, branched, or cyclic alkylgroup having 1 to 18 carbon atoms, a linear or branched, alkenyl grouphaving 1 to 18 carbon atoms, an aryl group, or an alkaryl group having 7to 18 carbon atoms; R³ is hydrogen, alkynyl, or a linear, branched, orcyclic alkyl group having 1 to 18 carbon atoms, a linear or branched,alkenyl group having 1 to 18 carbon atoms, an aryl group, or an alkarylgroup having 7 to 18 carbon atoms; R⁴ is silyl, silane, or siloxane, ora hydrocarbon group having the formula

wherein a is 0 or 1 and R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independentlyhydrogen, alkynyl, or a linear, branched, or cyclic alkyl group having 1to 18 carbon atoms, a linear or branched, alkenyl group having 1 to 18carbon atoms, an aryl group, or an alkaryl group having 7 to 18 carbonatoms;

wherein R^(2′), R^(3′), and R^(4′) are as defined for R², R³, and R⁴respectively; R¹⁴ is glycidyl, allyl, or a linear, branched, or cyclicalkyl, aryl, or alkaryl group comprising an oxirane or allyl moiety; αis an integer of 1 to about 100, or where R¹¹ is the ketal residue a is0 or an integer of 1 to about 100; and where there is more than one α,the values of α are the same or different; and β is an integer of 1 toabout
 10. 37. The compound of claim 36 wherein R¹, R¹⁴, or both furthercomprise one or more halogen, tertiary amine, amide, carbonate, ether,ester, keto, ketal, or urethane functionalities.
 38. The compound ofclaim 36 wherein β is 1 or
 2. 39. The compound of claim 36 wherein R² is—(CH₂)₂—, and R³ is —CH₃, and R⁴ is the residue of glycerol.
 40. Thecompound of claim 36 wherein about 20% by weight or more of the compoundis biomass based.
 41. The compound of claim 36 wherein between about 20%and 90% by weight of the compound is biomass based.
 42. The compound ofclaim 36 wherein between about 40% and 75% by weight of the compound isbiomass based.
 43. The compound of claim 36 wherein the compound isbiodegradable.
 44. A formulation comprising a. a compound of claim 36,and b. a free radical initiator, an alcohol, an amine, a vinyl compound,an oxiranyl compound, a chain transfer agent, a filler, a solvent, apolymer, a surfactant, a UV stabilizer, a thermal stabilizer, anantioxidant, a colorant, a plasticizer, a fiber, or a bleachingcompound, or a combination of two or more thereof.
 45. The formulationof claim 44 wherein the vinyl compound comprises acrylic acid,methacrylic acid, an alkyl acrylate, an alkyl methacrylate, and acrylatesalt, a methacrylate salt, acrylamide, methacrylamide, N-hydroxymethylacrylamide, methacryloxyethyl phosphate, acrylonitrile,methacrylonitrile, 2-acrylamido-2-methylpropanesulfonic acid or a saltthereof, maleic acid, maleic anhydride, an alkyl maleate, a maleatesalt, glycidyl methacrylate, hydroxyethyl methacrylate, hydroxypropylmethacrylate, chloro acrylic acid, an alkyl chloroacrylate; ethylene,propylene, an α-olefin such as α-hexene or α-octene, vinyl toluene,divinyl benzene, styrene, α-methyl styrene, t-butyl styrene,chlorostyrene, or a monohydric or polyhydric alcohol ester of acrylicand alkylacrylic acid such as ethylene glycol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, 1,3 butylenedimethacrylate, ethylene glycol diacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate, or pentaerythritoltetraacrylate; prop-2-enyl heptanoate, prop-2-enoxybenzene, prop-2-enylacetate, allyl vinyl ether, allyl methyl ether, bisallyl ether, allyladipate, diallyl carbonate, pentaerythritol tetraallyl ether,1-N,4-N-bis(prop-2-enyl)benzene-1,4-dicarboxamide, or a combinationthereof.
 46. The formulation of claim 44 wherein the oxiranyl compoundis2-[[4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane.47. (canceled)
 48. A compound having structure IV:

wherein R¹ is hydrogen or a monovalent, divalent, or multivalent linear,branched, or cyclic alkyl group having 1 to 18 carbon atoms, amonovalent, divalent, or multivalent linear or branched, alkenyl grouphaving 1 to 18 carbon atoms, a monovalent, divalent, or multivalent arylgroup, or a monovalent, divalent, or multivalent alkaryl group having 7to 18 carbon atoms; R² is a covalent bond or a linear, branched, orcyclic alkyl group having 1 to 18 carbon atoms, a linear or branchedalkenyl group having 1 to 18 carbon atoms, an aryl group, or an alkarylgroup having 7 to 18 carbon atoms; R³ is hydrogen, alkynyl, or a linear,branched, or cyclic alkyl group having 1 to 18 carbon atoms, a linear orbranched alkenyl group having 1 to 18 carbon atoms, an aryl group, or analkaryl group having 7 to 18 carbon atoms; R⁴ is a group having theformula

wherein a is 0 or 1 and R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independentlyhydrogen, alkynyl, or a linear, branched, or cyclic alkyl group having 1to 18 carbon atoms, a linear or branched alkenyl group having 1 to 18carbon atoms, an aryl group, or an alkaryl group having 7 to 18 carbonatoms; R¹⁵ is a repeat unit comprising the residue of a polymerized orgrafted acrylyl, alkacrylyl, glycidyl, or allyl group, or a linear,branched, or cyclic alkyl, aryl, or alkaryl group comprising the residueof a polymerized or grafted acrylyl, alkacrylyl, oxiranyl, or allylmoiety; α is an integer of 1 to about 100, and where there is more thanone α, the values of α are the same or different; and β is an integer ofabout 1 to
 10. 49. The compound of claim 48 wherein R¹, R¹⁵, or bothfurther comprise one or more halogen, tertiary amine, amide, carbonate,ether, ester, keto, ketal, or urethane functionalities.
 50. The compoundof claim 48 wherein β is 1 or
 2. 51. The compound of claim 48 wherein R²is —(CH₂)₂—, and R³ is —CH₃, and R⁴ is the residue of glycerol.
 52. Thecompound of claim 48 wherein R¹⁵ comprises the residue of a polymerizedacrylate, alkacrylate, or allyl group and further comprises a vinylcompound comprising acrylic acid, methacrylic acid, an alkyl acrylate,an alkyl methacrylate, and acrylate salt, a methacrylate salt,acrylamide, methacrylamide, N-hydroxymethyl acrylamide,methacryloxyethyl phosphate, acrylonitrile, methacrylonitrile,2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, maleicacid, maleic anhydride, an alkyl maleate, a maleate salt, glycidylmethacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate,chloro acrylic acid, an alkyl chloro acrylate; ethylene, propylene, anα-olefin such as α-hexene or α-octene, vinyl toluene, N-vinyl acetate,vinyl pyrrolidone, divinyl benzene, styrene, α-methyl styrene, t-butylstyrene, chlorostyrene, or a monohydric or polyhydric alcohol ester ofacrylic and alkylacrylic acid such as ethylene glycol diacrylate, 1,6hexane diol diacrylate, neopentyl glycol diacrylate, 1,3 butylenedimethacrylate, ethylene glycol diacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate, or pentaerythritoltetraacrylate; prop-2-enyl heptanoate, prop-2-enoxybenzene, prop-2-enylacetate, allyl vinyl ether, allyl methyl ether, bisallyl ether, allyladipate, allyl acetate, diallyl carbonate, pentaerythritol tetraallylether, 1-N,4-N-bis(prop-2-enyl)benzene-1,4-dicarboxamide, or acombination thereof.
 53. The compound of claim 48 wherein R¹⁵ is theresidue of a polymerized oxiranyl group, further comprising the residueof a polymerized oxiranyl compound, wherein the oxiranyl compoundcomprises2-[[4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane.54. The compound of claim 48 wherein R¹⁵ is a grafted residue furthercomprising a grafted surface, the grafted surface comprising a particlesurface, a solid macroscopic surface, or a coating surface.
 55. Thecompound of claim 54 wherein R¹⁵ is both a polymerized and graftedresidue.
 56. The compound of claim 48 wherein about 20% by weight ormore of the compound is biomass based.
 57. The compound of claim 48wherein between about 20% and 90% by weight of the compound is biomassbased.
 58. The compound of claim 48 wherein between about 40% and 75% byweight of the compound is biomass based.
 59. The compound of claim 48wherein the compound is biodegradable.
 60. A formulation comprising a. acompound of claim 48, and b. a filler, a solvent, a polymer, asurfactant, the residue of a crosslinker, a UV stabilizer, anantioxidant, a thermal stabilizer, a colorant, a plasticizer, atoughener, a tackifier, a fiber, or a bleaching compound, or acombination thereof.
 61. (canceled)
 62. The formulation of claim 60wherein the polymer comprises polyethylene terephthalate, polybutyleneterephthalate, polybutylene terephthalate adipate, polybutyleneterephthalate succinate (PBTS), polybutylene terephthalate glutarate,polylactic acid, poly-ε-caprolactone, poly-3-hydroxybutyrate,poly-4-hydroxybutyrate, polyhydroxybutyrate-valerate,polyhydroxybutyrate-propanoate, polyhydroxybutyrate-hexanoate,polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate,polyhydroxy-butyrate-hexadecanoate, polyhydroxybutyrate-octadecanoate,polyalkylene succinate, polyalkylene adipate, polystyrene,acrylonitrile-butadiene-styrene terpolymer, a polyisoprene rubber,polybutadiene, poly(vinyl alcohol), poly(vinyl acetate),poly(chloroethylene), a polyurethane, a polycarbonate, a polyacrylate, apolymethacrylate, a polyamide, polyethylene, polypropylene, a copolymerof any of these, or a blend of one or more thereof.
 63. An articlecomprising the compound of claim 48 wherein the article comprises acontainer, a transparent windowpane, a fiber reinforced composite part,a film, a fiber, a foam, a coating, or a laminate.
 64. A compound havingstructure V:

wherein R² is a covalent bond or a linear, branched, or cyclic alkylgroup having 1 to 18 carbon atoms, a linear or branched alkenyl grouphaving 1 to 18 carbon atoms, an aryl group, or an alkaryl group having 7to 18 carbon atoms; R³ is hydrogen, a linear, branched, or cyclic alkylgroup having 1 to 18 carbon atoms, a linear or branched alkenyl grouphaving 1 to 18 carbon atoms, an aryl group, or an alkaryl group having 7to 18 carbon atoms; R⁴ is silyl, silane, or siloxane, or a hydrocarbongroup having the formula

wherein a is 0 or 1 and R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are independentlyhydrogen, alkynyl, or a linear, branched, or cyclic alkyl group having 1to 18 carbon atoms, a linear or branched alkenyl group having 1 to 18carbon atoms, an aryl group, or an alkaryl group having 7 to 18 carbonatoms; R¹¹ is a monovalent, divalent, or multivalent linear, branched,or cyclic alkyl group having 1 to 36 carbon atoms, a monovalent,divalent, or multivalent linear or branched alkenyl group having 1 to 36carbon atoms, a monovalent, divalent, or multivalent aryl group, analkaryl group having 1 to 36 carbon atoms, or a ketal residue comprisingthe structure

wherein R^(2′), R^(3′), and R^(4′) are as defined for R², R³, and R⁴respectively; R¹⁶ is a repeat unit comprising the residue of apolymerized or grafted glycidyl or allyl group, or a linear, branched,or cyclic alkyl, aryl, or alkaryl group that includes the residue of apolymerized or grafted oxiranyl or allyl moiety; α is an integer of 1 toabout 100, or where R¹¹ is a ketal residue α is 0 or an integer of 1 toabout 100; and where there is more than one α, the values of α are thesame or different; and β is an integer of 1 to about
 10. 65. Thecompound of claim 64 wherein R¹, R¹⁶, or both further comprise one ormore halogen, tertiary amine, amide, carbonate, ether, ester, keto,ketal, or urethane functionalities.
 66. The compound of claim 64 whereinβ is
 2. 67. The compound of claim 64 wherein R² is —(CH₂)₂—, and R³ is—CH₃, and R⁴ is the residue of glycerol.
 68. The compound of claim 64wherein R¹⁶ comprises the residue of a polymerized allyl group andfurther comprises a vinyl compound, the vinyl compound comprisingacrylic acid, methacrylic acid, an alkyl acrylate, an alkylmethacrylate, and acrylate salt, a methacrylate salt, acrylamide,methacrylamide, N-hydroxymethyl acrylamide, methacryloxyethyl phosphate,acrylonitrile, methacrylonitrile, 2-acrylamido-2-methylpropanesulfonicacid or a salt thereof, maleic acid, maleic anhydride, an alkyl maleate,a maleate salt, glycidyl methacrylate, hydroxyethyl methacrylate,hydroxypropyl methacrylate, chloro acrylic acid, an alkyl chloroacrylate; ethylene, propylene, an α-olefin such as α-hexene or α-octene,vinyl toluene, divinyl benzene, styrene, α-methyl styrene, t-butylstyrene, chlorostyrene, or a monohydric or polyhydric alcohol ester ofacrylic and alkylacrylic acid such as ethylene glycol diacrylate, 1,6hexane diol diacrylate, neopentyl glycol diacrylate, 1,3 butylenedimethacrylate, ethylene glycol diacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate, or pentaerythritoltetraacrylate; prop-2-enyl heptanoate, prop-2-enoxybenzene, prop-2-enylacetate, allyl vinyl ether, allyl methyl ether, bisallyl ether, allyladipate, diallyl carbonate, pentaerythritol tetraallyl ether,1-N,4-N-bis(prop-2-enyl)benzene-1,4-dicarboxamide, or a combinationthereof.
 69. The compound of claim 64 wherein R¹⁶ is the residue of apolymerized glycidyl group or oxiranyl moiety, and further comprises theresidue of a polymerized oxiranyl compound, wherein the oxiranylcompound comprises2-[[4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane.70. The compound of claim 64 wherein R¹⁶ is a grafted residue furthercomprising a grafted surface, the grafted surface comprising a particlesurface, a solid macroscopic surface, or a coating surface.
 71. Thecompound of claim 70 wherein R¹⁶ is both a polymerized and graftedresidue.
 72. The compound of claim 64 wherein about 20% by weight ormore of the compound is biomass based.
 73. The compound of claim 64wherein between about 20% and 90% by weight of the compound is biomassbased.
 74. The compound of claim 64 wherein between about 40% and 75% byweight of the compound is biomass based.
 75. The compound of claim 64wherein the compound is biodegradable.
 76. A formulation comprising a. acompound of claim 64, and b. a filler, a solvent, a polymer, asurfactant, the residue of a crosslinker, a UV stabilizer, a thermalstabilizer, an antioxidant, a toughener, a tackifier, a colorant, aplasticizer, or a bleaching compound, or a combination thereof.
 77. Theformulation of claim 76 wherein the formulation is suitable for coating,spraying, thermoforming, or cutting.
 78. The formulation of claim 76wherein the polymer comprises polyethylene terephthalate, polybutyleneterephthalate, polybutylene terephthalate adipate, polybutyleneterephthalate succinate (PBTS), polybutylene terephthalate glutarate,polylactic acid, poly-ε-caprolactone, poly-3-hydroxybutyrate,poly-4-hydroxybutyrate, polyhydroxybutyrate-valerate,polyhydroxybutyrate-propanoate, polyhydroxybutyrate-hexanoate,polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate,polyhydroxy-butyrate-hexadecanoate, polyhydroxybutyrate-octadecanoate,polyalkylene succinate, polyalkylene adipate, polystyrene,acrylonitrile-butadiene-styrene terpolymer, a polyisoprene rubber,polybutadiene, poly(vinyl alcohol), poly(vinyl acetate),poly(chloroethylene), a polyurethane, a polycarbonate, a polyacrylate, apolymethacrylate, a polyamide, polyethylene, polypropylene, a copolymerof any of these, or a blend of one or more thereof.
 79. An articlecomprising the compound of claim 64 wherein the article comprises acontainer, a transparent windowpane, a fiber-reinforced composite part,a film, a fiber, a foam, a coating, or a laminate.
 80. The compound ofclaim 1 wherein R² is —(CH₂)₂—, R³ is —CH₃, and R⁴ is the residue ofglycerol; R¹¹ is the residue of a diacid, the diacid comprising oxalicacid, malonic acid, succinic acid, adipic acid, pimellic acid, subericacid, dodecane-dioic acid, azelaic acid, a dimer acid, sebacic acid, oro,m, or p-phthalic acid; and β is
 2. 81. The compound of claim 1 whereinR² is —(CH₂)₂—, R³ is —CH₃, and R⁴ is the residue of glycerol; and βis
 1. 82. The compound of claim 9 wherein R² is —(CH₂)₂—, R³ is —CH₃,and R⁴ is the residue of glycerol; and one or more α, α′, or both areindependently between 0 and about
 5. 83. The compound of claim 82wherein compound IA, IB, or both further comprise hydroxyl functionalendgroups.
 84. The compound of claim 24 wherein R² is —(CH₂)₂—, R³ is—CH₃, and R⁴ is the residue of glycerol; and β is 1 or
 2. 85. Thecompound of claim 36 wherein R² is —(CH₂)₂—, R³ is —CH₃, and R⁴ is theresidue of glycerol; and β is 1 or
 2. 86. The compound of claim 48wherein R² is —(CH₂)₂—, R³ is —CH₃, and R⁴ is the residue of glycerol;and β is 1 or
 2. 87. The compound of claim 64 wherein R² is —(CH₂)₂—, R³is —CH₃, and R⁴ is the residue of glycerol; and β is 2.